Caustic Soda Manual

NaOH
Caustic Soda
PPG Industries, Inc.
©2008 PPG Industries, Inc.

C H A P T E R
DANGER!
Caustic Soda Can Cause Severe Burns to Skin and Eyes
Caustic soda (also called lye or sodium hydroxide) attacks the skin and eyes rapidly. Even a small
quantity of a dilute solution can severely injure the eyes or cause blindness. Overexposure to
caustic soda by way of skin burns or swallowing can cause death.
Persons working with caustic soda should wear protective clothing and close-fitting
goggles at all times.
Caustic soda is a reactive chemical and can react with certain other chemicals and
metals to produce explosions.
Read Chapter 3 for more information on the hazards of caustic soda, on protective devices
and on first aid.
In case of emergency, call PPG Industries Emergency Response Center
at (412) 434-4515. This telephone is answered 24 hours a day.
SODIUM SODIUM
HYDROXIDE HYDROXIDE
LIQUID SOLID
UN 1824 UN1823
EMERGENCY TELEPHONE NUMBER

PPG INDUSTRIES, INC. (412) 434-4515
NaOH
In Canada call CANUTEC (613) 996-6666
2
Table of Contents
CHAPTER PAGE
1. Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 4
2. Purchasing Information . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 6
Caustic Soda Liquor
PELS® Caustic Soda Beads
3. Protective Devices and First Aid . . . . . . . . . . . . . . . . . . . . . . . . . . 10
4. Caustic Soda Liquor . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 13
Handling and Storage Equipment
5. Caustic Soda Liquor . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 17
Unloading and Handling
6. PELS Caustic Soda Beads. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 23
7. Technical Data . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 26
8. Methods of Analysis . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 48
9. Uses of Caustic Soda . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 56
10. Methods of Manufacture . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 57
3 NaOH
©PELS is the registered trademark of PPG Industries for its brand of beaded caustic soda.
C H A P T E R 1
Introduction
austic soda is a hazardous, Other PPG rail cars and truck trailers closed system delivery of bulk, dry
C reactive chemical. Before

persons work with caustic
soda, they should be instructed in
are available for delivery of PELS®
caustic soda beads. PPG barges serve
customers on rivers and inland water-
caustic soda in pressure-differential
hopper cars and truck trailers, and
PELS caustic soda beads.
safe handling practices and first aid, ways, while coastal terminals are
and should wear the recommended supplied by ocean-going tankers. PPG is positioned to meet its cus-
protective clothing and equipment tomers’ needs for material—and
(see chapter 3). •Stocks of PELS caustic soda beads service.
are maintained at strategically locat-
PPG Industries, one of the world’s ed distribution points throughout the A network of caustic soda distribution
largest producers and suppliers of nation. points assures quick delivery.
caustic soda, has three caustic plants
strategically located in the United •PPG Industries sales representa-
States and Canada. These plants serve tives, thoroughly trained to serve
a large and highly diversified group of caustic soda customers, operate
consumers located throughout North from offices located in major cities
America and worldwide. In addition, throughout the United States, Puerto
PPG is the only domestic producer of Rico and Canada.
beaded caustic soda . •PPG engineers provide assistance to
The combination of high-volume caus- customers by offering a full range of
tic soda production plus orientation as technical information and consulta-
a supplier of caustic soda to North tion. Their services include: sharing
America enables PPG to back up its information on systems for unload-
product with a coordinated system of ing, handling and storing various
services important to all caustic soda caustic soda forms; assistance in
consumers. startups and trouble-shooting; advice
on form and grade selection.
•A network of bulk terminals
for shipment of liquid caustic soda is •Other activities encompass techni-
operated in North America. Overnight cal service engineering assistance
service to many in selecting and installing handling
customers is made possible equipment and protective devices as
by this system of bulk terminals. well as help with safety training pro-
grams. These include providing
•Versatile shipping capabilities safety wall charts, booklets and
include tank car, tank truck, barge other literature. PPG’s position as
and ocean-going tanker transporta- a front-running caustic producer is
tion of caustic soda. PPG owns maintained by an extensive program
hundreds of tank cars designed and of research and development. Its
NaOH
used exclusively for caustic soda results include many benefits that
solution service. are passed on to customers. Other
technical advances include “CSD,”
4
C H A P T E R 1
Shipping Points
SHIPPING POINTS FOR CAUSTIC Tank Cars and Tank Trucks Barges
SODA SOLUTIONS: Illinois: Lemont Louisiana: Lake Charles
Louisiana: Lake Charles West Virginia: Natrium
Missouri: St. Louis
New Jersey: Bayonne
West Virginia: Natrium Ocean-going Tankers
Canada: Beauharnois, Quebec Louisiana: Lake Charles
Puerto Rico: Guayanilla
(tank trucks only)
Tank Cars and Tank Trucks

■ Barges
✴ Ocean-going Tankers
5 NaOH
C H A P T E R 2
Purchasing Information
austic soda is a hazardous, Representatives of PPG Industries will

gladly cooperate in determining the
most economical and best-suited
grade and form for any operation.
safe handling practices and first aid,
and should wear the recommended CAUSTIC SODA
protective clothing and equipment SOLUTIONS
(see chapter 3).
Shipping
GRADES AND FORMS Caustic soda solutions are shipped
To meet the needs of various industrial from PPG manufacturing plants as
processes, the Chemicals Group of 50 percent solutions and 73 percent
PPG Industries produces caustic soda solutions by weight. The company’s
in a wide range of grades and forms. nationwide network of terminals
Caustic soda solutions are available in stocks 50 percent solutions in strategic
these grades: geographic locations for prompt deliv-
•standard PELS caustic soda beads show little
ery to many parts of the United States.
•purified or no dust.
PPG Industries ships 50 percent
•diaphragm caustic soda solution in ocean-going
•membrane PPG Industries manufactures anhy-
tankers to terminals on the east and
•mercury cell drous caustic soda in the modern
west coasts for domestic users as
beaded form bearing the trademark
The most common commercial form is well as for export. The company’s
PELS. The beads come in one opti-
the solution containing 50% actual large fleet of barges carries caustic
mum size averaging 0.7 millimeter in
sodium hydroxide by weight. A 25% soda solutions to inland and coastal
diameter. Their size uniformity is an
form is also available from the Natrium terminals and customers’ docks.
advantage for repacking and com-
plant. PPG Industries also produces pounding. Their one optimum size PPG engineers will assist companies
the more concentrated solution form, eliminates the need to store numerous in evaluating new unloading facilities
approximately 73% actual sodium grades of anhydrous caustic soda. for tank cars, tank trucks or barges.
hydroxide by weight.
SELECTING THE OPTIMUM
GRADE AND FORM
Among the factors in selecting the
most economical grade and form of
caustic soda for a particular applica-
tion, besides purchase price, are the
costs of: transportation, unloading,
NaOH
handling within plant, preparing caus-
tic soda for use, and the investment
in equipment for unloading, storage,
handling and preparation.
Liquid caustic soda available in Loading caustic soda solution into tank car.
6 25%, 50% and 73% solutions.
C H A P T E R 2
Typical Weights to 4,000 gallons. For shipments of 50
of Tank Car Contents percent caustic soda solutions, the
corresponding weights would range
Nominal Capacity, Gallons from 25,000 to 50,000 pounds of
10,000 16,000 liquid. On an anhydrous basis, these
Liquid basis shipping weights would range from
50 percent 128,000 lb 194,000 lb 6 to 12 tons.
73 percent 142,000 lb 200,000 lb
Loading caustic soda solution into an ocean- Anhydrous basis
going tanker at PPG•plant in Lake Charles,
Louisiana.
50 percent 33 tons 50 tons
73 percent 52 tons 73 tons
To prevent metallic contamination and
maintain the high purity of caustic
soda shipments, PPG lines all cargo
tanks of tank cars and barges. Dimensions of Tank Cars
10,000-gallon 16,000-gallon
Tank Cars
Length 41’ 2” 43’ 3 3/8”
PPG maintains a fleet of many hun- Height
dreds of tank cars for caustic soda Empty 14’ 7 ¾” 14’ 10 5/8”
service only. They are specifically Loaded 14’ 5 ¾” 14’ 8 5/8”
designed for the unloading of caustic Width 10’ 7 ½” 10’ 0” PPG•barge dedicated to shipping caustic
soda solution.
soda solutions. Every PPG tank car is
equipped for either top or bottom Tank Trucks
unloading. Barges
Tank trucks provided by common car-
PPG tank cars are well insulated, so riers for the shipment of caustic soda The barges in the fleet of PPG
that freezing is unlikely except under solutions must conform to applicable Industries are built specifically for
non-routine conditions such as pro- specifications. PPG will not load into transporting caustic soda solutions.
low-pressure trailers. Tanks are gener- They are equipped with diesel unload-
ally made of stainless steel. Maximum ing pumps.
permissible loads may be limited by
Barge capacities range from a
regulations of the different states.
minimum of 1,200 liquid tons or
The capacities of tank trucks in caus- approximately 200,000 gallons up
tic soda service have not been to a nominal 3,000 liquid tons or
Caustic soda tank car. approximately 475,000 gallons.
standardized, but vary between 2,000
Since almost all barge shipments con-
longed transit delays. The cars are
sist of 50 percent caustic liquor, the
equipped with channel-type heaters if actual dry caustic soda content ranges
heating is required.
NaOH
from 500 to 1500 tons.
Shipments are usually made in tank
cars with nominal capacities of 10 and
16 thousand gallons.
7 Caustic soda tank truck at loading platform.
C H A P T E R 2
Shipping Points for Caustic Soda Therefore, the % Na2O content of the Bulk Shipments
Solutions NaOH and Na2CO3 in the shipment is
as follows: PELS caustic soda beads are shipped
See list with map on pages 4 and 5. % Na2O in NaOH in rail cars and truck trailers. The rec-
= 0.16% x 0.5848 = 0.09% ommended method of handling is the
Billing Procedure “CSD” closed system delivery method
Caustic soda solutions are billed on a Therefore, the total % Na2O is: developed by PPG Industries. It utilizes
basis that is standard in the United 38.74% + 0.09% = 38.83% Na20 a closed-loop, pneumatic system for
States. However, this basis is rather pressure conveying.
The billing analysis (% NaOH on a
complicated because of the way it 76% Na2O basis) is calculated as PPG maintains its own fleet of pres-
originated. Since the days when alka- follows: sure differential trailers that can make
lis were first manufactured, caustic shipments up to approximately 21
soda (NaOH) and soda ash (Na2CO3) Total % Na20 x 100%
tons. These trailers carry equipment
were compared on the basis of their 76% for drying the pneumatic conveying air
sodium oxide (Na2O) content. The so that the receiving system does not
anhydrous forms of caustic soda in or,
need to have dryers.
those days were about 98 percent 38.83 x 100
pure. According to the molecular 76% PPG Industries owns the pressure dif-
weights of NaOH and Na2O, 100 ferential rail cars used for CSD
pounds of pure NaOH are calculated to = 51.09% NaOH (76% Na2O basis) shipments. The rail cars are lined with
contain 77.48 pounds of Na2O. But the a caustic soda compatible protective
The pounds of NaOH (76% Na2O basis)
98 percent purity factor reduces this coating. These cars have a capacity of
used for invoicing are calculated as
value to 76 pounds. Today, liquid 3000 to 4000 cubic feet, sufficient for
follows:
caustic soda is still sold as “NaOH shipments up to 100 tons.
on a 76 percent Na2O basis.” Pounds Caustic Soda Solution
More detailed information on “CSD”
Another factor in billing is that the % NaOH (76% Na2O basis) closed system delivery appears on
Na2O content is determined by a labo- 100 page 24 in the chapter on PELS Caustic
ratory method which includes the Na2O Soda Beads Unloading and Handling.
in both NaOH and Na2CO3. The latter is = Pounds NaOH (76% Na2O basis)
present as a fractional percentage. Bag Shipments
PELS CAUSTIC SODA BEADS
For example, assume that a shipment PPG Industries can supply PELS caus-
of nominal 50 percent caustic soda PPG Industries supplies anhydrous tic soda beads on sturdy pallets
solution contains the following caustic soda in the beaded form bear- protected by a shrink-wrapped poly-
percentages by weight of NaOH ing the trademark PELS. Drums and ethylene film. This method of shipment
and Na2CO3: bags are designed to be moisture- can reduce damage in transit, permits
% Actual NaOH=50.00% resistant because anhydrous caustic outdoor storage, facilitates stacking
% Actual Na2CO3=0.16% soda readily absorbs moisture from pallet loads and protects the bags
NaOH
atmospheric air. from chemicals, moisture and dirt.
Based on their relative molecular
weights, NaOH contains 77.48% Na2O The bag has six walls including two
while Na2CO3 contains 58.48%. moisture barriers: a heat-sealed poly-
ethylene liner and a Valeron®
8
C H A P T E R 2
Drum Shipments PELS Caustic Soda
Container Net Weight, pounds
The common type of full open head
Steel drums 100, 500
steel drum has a flowed in or a rubber Bags 50, 2000
gasket to make the container mois- Fiber drums 500
ture-resistant.
Shipping Points
For PELS Caustic Soda
Louisiana: Lake Charles
West Virginia: Natrium
The entire palette load, (foreground) 1 1/2

tons, consisting of sixty 50-pound bags, is
protected by a shrink-wrapped polyethylene
film. PELS•Caustic Soda beads are also pack-
aged in steel and fiber drums (background). POLYETHYLENE LINER
50-POUND NATURAL
cross-laminated polyethylene ply (see KRAFT LAYER
photo). This bag exceeds Department 50-POUND NATURAL
KRAFT LAYER
of Transportation drop test standards
VALERON®
for multiwall packages. Accelerated PLASTIC BARRIER
tests in a “jungle room” showed that & STRENGTH LAYER
50-POUND NATURAL
moisture vapor did not reach the caus- KRAFT LAYER
tic soda. Drop tests performed after 50-POUND WET STRENGTH
the “jungle room” exposure showed NATURAL KRAFT LAYER
virtually the same results as before.
In comparison with older types of pil-
low-shaped bags, the rectangular bags Super-strong bag has six walls including two moisture barriers.
have better sag resistance and fewer
loose edges that provide easier han-
dling. The bags occupy less space
than older types of bags and permit
more compact unitizing and more sta-
ble pallet loads.
Rectangular bags take up only 73% of
the space occupied by round drums.
Drumming PELS caustic soda beads.

9
C H A P T E R 3
Protective Devices and First Aid
verconfidence can be A deceptive aspect of caustic soda is Eyes
O responsible for serious per-

sonal injuries from caustic
soda, especially to persons who
that a burning sensation is not always
immediately experienced on contact
with the skin. Serious damage may
Eyes are particularly sensitive to caus-
tic soda. Even tiny particles of caustic
soda dust, or a small quantity of dilute
have worked around caustic soda for therefore happen before a person is
many years without accident. aware of contact with caustic soda. If solution, can injure the eye or result in
Caustic solutions or particles in con- contact with caustic soda is suspect- blindness or permanent eye damage.
tact with the skin can cause severe ed, flush with water right away even If caustic soda gets in the eye,
burns. Even a small quantity in the though there is no burning sensation. flushing the eye immediately
eye may damage vision permanently. with large quantities of water
Persons working around caustic will do more good than the best
soda should wear protective of medical services can provide
clothing and close-fitting later on.
monogoggles at all times. Continue washing for at least
15 minutes. Call a physician.
Prevent Accidents
The prevention of accidents is the best To make sure that water contacts all
protection against injury. Equipment surface tissues of the eye and lid, hold
should be checked on a regular main- the eyelids apart while flushing. The
tenance schedule to prevent leaks and best way to irrigate the under surfaces
If caustic soda gets in the eye, flush eye of the upper eyelid is to raise the eye-
spraying of caustic soda liquor. immediately with large quantities of water.
Personnel should be trained in proper lid and roll it back. Prolonged irrigation
handling procedures. FIRST AID with plenty of water—and only
water—is the proper treatment for
Liquid spills should be cleaned up right All persons who handle caustic soda eyes. Neutralizing solutions must
away. They make a floor slippery, and should be familiar with proper first aid not be used in the eyes. Chemical
a person falling into a puddle of caus- procedures. neutralization generates heat and may
tic liquor can suffer extensive body introduce another burn hazard. Diluting
burns. Fast action is imperative because
caustic soda also generates heat; so
caustic soda attacks the skin and eye
Treat Immediately use plenty of water to conduct the
tissues rapidly. Delay greatly increases
heat away.
the severity of a caustic burn; prompt
Speed of treatment in case of con-
and thorough treatment can reduce the Call a physician, preferably an eye
tact with caustic soda is extremely
danger of serious permanent damage. specialist, as soon as possible.
important. Caustic soda reacts chemi-
Get the injured person to an eye Continue eye irrigation until the
cally with body tissue and will cause
wash or spray shower immediately! physician arrives.
severe burns unless it is washed off
Every second is critical. Be sure that
the skin with plenty of water immedi- Eye-Washing Fountains and
medical attention is obtained as
NaOH
ately. Clothing should be removed. Spray Showers
soon as possible if caustic soda has
Refer to Material Safety Data Sheet for
contacted an eye, also if skin con- The operation of eye wash fountains
caustic soda.
tact has resulted in burns, reddening and safety showers should be checked
or excessive irritation.
10
C H A P T E R 3
before wash begins. destroyed by caustic, whereas cotton 15 minutes—longer if a soapy feeling
Spray showers and eye- is more resistant. Leather, like wool persists, which indicates that some
washing fountains or a and animal tissues, is also attacked by caustic soda is still present. Do not
bubbler caustic. Wear shoes, boots or over- sponge or rub or use small amounts
fountain should be located shoes made of rubber. Also, wear a of water. Large quantities of water
in the immediate working plastic safety hard hat. The wide brim are necessary to carry away the heat
area where they can be style provides additional protection generated by diluting caustic soda. Do
reached in seconds. from overhead drips or leaks. Set the not touch your eyes with your hands
front of hat to slope down over eyes to or fingers—they might be contaminat-
Out-of-doors, a hose that is provide more cover for the eyes. ed with caustic soda.
not under high pressure can When boots are worn, trouser legs
serve temporarily in place should be on the outside to reduce the Caustic soda burns can be most
of a shower or eye-washing possibility that caustic soda might deceiving. A grave danger lies in stop-
fountain. enter the top opening. Wear a long- ping the flushing with water too soon.
sleeved shirt and button the collar. What may first appear to be a superfi-
Eyewash Prominent markings to cial skin irritation can become a
fountain. make the location of Shirt or coveralls
should fit snug at serious burn that may take a long time
safety showers and fountains to heal. The greater the amount and
distinctly visible by means of a sign neck and wrists.
concentration of the caustic soda and
or conspicuous background color are Respirator its temperature, the more imperative it
recommended. Showers and fountains is to get to a source of water immedi-
should be tested daily and kept clean Persons working ately.
and in perfect working order at where caustic soda
all times. dust or mist is Under the safety shower, remove
present should clothing that has been in contact with
Protective Clothing wear NIOSH/MSHA- caustic. Continue flushing while
All persons working around caustic approved dust-type removing clothing. Do not remove
soda should wear protective clothing respirators. safety goggles unless caustic soda
as well as close-fitting safety gog- Inhalation of dust or has been washed off completely under
gles. Do not wear contact lenses mist will irritate the the shower. Anyone helping a person
when working around caustic soda. respiratory tract. with caustic soda on their body or
Proper protective The OSHA permissi- clothing should wear safety goggles to
Face shields may be worn in addition clothing reduces
to—but not instead of—goggles. chances of injury. ble exposure limit make sure that their own eyes don’t
Gloves, boots aprons, and other cloth- (PEL) for caustic get splashed with water contaminated
ing made of rubber or rubber-covered soda is a ceiling value of 2 milligrams by caustic soda.
cloth give good protection because per cubic meter of air. Work areas
where caustic soda dust or mist is A less serious condition, stinging due
rubber is resistant to caustic soda. to caustic soda mist or dust on
present should be well ventilated.
Clothing made of polyvinyl chloride exposed skin, can be stopped by rins-
NaOH
also gives good protection. Under the Skin ing with a 10% solution of ammonium
protective clothing, wear cotton cloth- chloride. Diluted vinegar may also be
Flush skin immediately and continu- used to stop stinging. Do not use neu-
ing rather than woolens, because ously with plenty of water for at least
animal fibers such as wool are rapidly tralizing solutions in the eye.
11
C H A P T E R 3
Swallowing
If a person swallows caustic soda,
give plenty of water to drink.
Afterwards, citrus juices or weak vine-
gar solutions may also be given. Do
not induce vomiting because passing
the caustic soda through the food
pipe, throat and mouth a second time
will result in more damage to these
tissues. Caustic soda causes severe
damage to mucous membranes. If a
person has swallowed caustic soda,
call a physician at once. Don’t give
anything by mouth to an uncon-
scious person.
Shock
If a patient suffers from shock, place
them on their back and keep them
warm until a doctor arrives.
12 NaOH
CHAPTER 4
Caustic Soda Liquor Handling
and Storage Equipment
austic soda is a hazardous,

and should wear the recommended
protective clothing and equipment
(see chapter 3).
MATERIALS OF
CONSTRUCTION
Iron and steel are the usual materials of
construction for equipment handling 50
percent solutions of caustic soda below
140° F. Nickel, nickel alloys and stainless
steel are required at higher tempera-
tures, for higher concentrations, or for
operations where iron pickup of a few
parts per million cannot be tolerated.
To prevent metallic contamination in
transit, more than one type of liner is
used on the interior of tank cars and
barge tanks. Tank trucks are ordinarily
constructed of stainless steel but their Corrosion Rates in 50% NaOH
interiors may also be lined.
Corrosion Rate, Mpy
Designers of equipment for handling
Metal At 100°Fa At 135°Fb At 131 to 167°Fc
and storing caustic soda may want to Titanium <0.1 0.5 ….
evaluate other materials and new Zirconium <0.1 <0.1 ….
products. PPG engineers will share Nickel <0.1 <0.1 <0.1
information on request regarding the Moneld alloy 400 <0.1 <0.1 <0.1
selection of construction materials for Inconeld alloy 600 <0.1 <0.1 <0.1
individual applications. Ampcoe 8 …. 1 ….
Mild steel 0.7 5 8
Stress-Corrosion Failure Copper-nickel (70-30) …. …. <0.1
Commonly called “caustic embrittle- 18-8 stainless steel …. …. 0.1
ment,” stress-corrosion failure occurs Ni-Resistf Type 1 …. …. 2
NaOH
Cast iron …. …. 10.5
at areas of mechanical stress or
where fabricating operations produce
high residual stress such as at bends a
Duration of test: 162 days. bDuration of test: 135 days. cDuration of test: 30 days.
in piping and at welds. d
Trademark of The International Nickel Co., Inc. eTrademark of Ampco Metal, Inc.
f
Trademark of Thomas Foundries, Inc.
13
CHAPTER 4
As shown in the graph, mild steel is Copper can seriously contaminate there is danger that caustic liquor
subject to stress-corrosion failure caustic soda even though it may not might drip and contact personnel.
under conditions that depend upon be severely attacked. Caustic handling
temperature and also upon concentra- equipment made with copper or cop- New piping installations should
tion. These conditions would exist in per alloys can be harmful to certain always be tested with water for leaks
the area above the curve in the graph. manufacturing processes, such as the before caustic liquor is introduced into
To prevent stress-corrosion failure, production of hypochlorite bleaches, the piping. Plastic covers on flanged
temperatures of 50 percent caustic because of their great sensitivity to joints, also guards over pump packing
soda solutions should not be permitted copper contamination. glands, prevent spraying of caustic
to go above 140° F. liquor if leaks develop.
PIPE LINES Process piping under 1-inch diameter
MATERIALS ATTACKED is not recommended. Larger sizes per-
BY CAUSTIC SODA Wrought iron or mild steel is suitable mit greater flow-through and minimize
for pipelines and fittings to convey the possibility of plugging or freezing.
Certain metals, such as aluminum, caustic soda solutions below 140°F;
magnesium, zinc, tin, chromium, nickel is customary for hotter solu- Unloading Lines
brass, and bronzes made with zinc or tions. Monel alloy or stainless steel
tin are attacked by caustic soda. They may be used under certain conditions. Tank car unloading lines are usually 2-
should be avoided as parts of equip- Polypropylene-lined steel pipe has inch diameter pipe because this is the
ment; for example, brass bearings. been used with solutions up to 225°F. standard fitting size on caustic soda
Also items such as safety hats, buck- Outdoor pipes should be insulated and, tank cars.
ets, drums and ladders made of if air temperatures fall below 65°F, Flexible hoses are preferred for con-
aluminum should not be used with electrically-traced. Welded or flanged necting a tank car to the unloading
caustic soda. joints are preferable to screwed fittings. pipe line because the car rises during
Since galvanizing is done with zinc— Many different types of plastics and unloading. Spiral-wire-wound hoses
which is attacked by caustic elastomers may be used with caustic made of alkali-resistant material are
soda—keep the liquor away from gal- liquor but the upper temperature limit, suitable. These hoses should have
vanized iron surfaces. The reaction of of course, is different for each plastic. clamped “combination nipple” ends
caustic soda with zinc is vigorous Do not use rubber gaskets. Materials made of cadmium-plated malleable
and—under some conditions—may whose capabilities for caustic serv- iron. Hoses may also be made of
be dangerous because hydrogen is ice have not been established by stainless steel.
generated and may introduce an experience should be adequately
explosion hazard. tested in advance. PUMPS
Silica-containing materials such as Pipe lines should slope so as to be For transferring caustic liquor from
glass, brick and tile are attacked by self-draining. Caustic liquor left in pipe tank car to storage or from storage to
caustic liquor. The action is slow and lines has a passivating effect and point of use, centrifugal pumps are
will at first only contaminate the caus- retards corrosion; however, it should recommended. All-iron construction is
NaOH
tic with silica, but failure of the not be left in pipe lines if temperatures generally suitable, although nickel and
material will eventually follow. may reach the freezing point of the nickel-cast-iron pumps give longer
solution. Water should be available for service life. Above 140°F, a nickel or
washing out sections of line where nickel alloy pump must be used. Brass
14
CHAPTER 4
fittings and bearings should be avoided, rials resistant to caustic soda solu- peratures far above 290°F, the boiling
especially at high temperatures or tions. Meters with brass parts, such point of a 50% solution of caustic
concentrations of 50% or above. To as used in water meters, would be soda. Coils located too near the side of
prevent leakage at the pump shaft, corroded by caustic soda. Suitable the tank are known to have caused
deep stuffing glands with high-grade meters are available with attachments stress-cracking as well as accelerated
TFE impregnated carbon fiber packing to compensate for changes of specific corrosion of the tank walls. Piping and
are preferred to mechanical seals. gravity with temperature where this storage systems should be checked
Mechanical seals are only recom- degree of accuracy is required. throughout to make sure that local
mended after consultation with the overheating will not occur.
seal manufacturer. The selection includes automatic and
semi-automatic meters for continuous Both metallic contamination and
or batch operations. They range in stress-corrosion can be eliminated by
VALVES capacity from 0.1 gallon per minute to a special coating applied to the inside
Use Teflon® brand fluoropolymer hundreds of gallons per minute. of the tank, such as epoxy-phenolic
resin-lined plug valves, which are (Carboline Plasite 9570) or novalac‑
PPG engineers will share information epoxy (PPG Amercoat 253). It should
gear-operated above the 4” size. Iron on request regarding the type and size
or steel plug valves of the lubricated be applied by licensed applicators only.
of meter required for any installation.
type give good service for normal use. Areas of unrelieved high stress, such
For high-temperature use, nickel-cast- as welds, are susceptible to caustic
iron plug valves or nickel gate valves STORAGE TANKS
attack. Many tanks can be completely
with deep packing glands should be The most popular construction materi- stress-relieved by the fabricator; the
used. Stainless steel can also be used al for storage tanks holding caustic cost may be considered as insurance
in some cases. soda solutions is mild steel because of against failure. Many welds made in
Other types of valves commonly its lower cost and satisfactory per- the field have been locally stress-
used include non-lubricated ball formance under most conditions. relieved with satisfactory results.
valves and gate valves made entirely The 50% solution should be stored at Preventing Freezing
of iron or steel. 75 to 100°F. Below 75°F, viscosity
increases rapidly and pumping The storage temperature of 50% caus-
Brass valves should be avoided, tic soda solutions should not go below
especially at high temperatures or becomes difficult. Above 140°F, iron
pickup increases and stress-corrosion 75°F. At lower ambient temperatures,
concentrations of 50% or above, tanks should be insulated. If these
because they are corroded by caustic cracking may become a problem.
solutions are stored out-of-doors in
soda and will leak. They can also Preventing Caustic Attack cold climates, the tanks should be
introduce copper contamination that and Iron Pickup insulated and heated. Steam coils
can be harmful to certain manufactur- made of nickel submerged in the solu-
ing processes. Even localized high temperature can
tions are the usual method of heating.
accelerate caustic attack. For exam-
A small steam or hot water heat
METERS ple, heating coils carrying steam will
exchanger and circulating pump can
NaOH
have a surface temperature of at least
also be used.
There are several types and designs of 212°F. Coils made of nickel or nickel
highly accurate meters with excellent alloys such as Monel and Inconel are If storage capacity is available, dilution
reproducibility that are made of mate- highly resistant to attack even at tem- is an effective way to avoid freezing
15
CHAPTER 4
problems. For example, a 20% solution

freezes at approximately—17°F.
Tank Capacity and Strength
Storage capacity should exceed the
volume of the largest shipment
planned by at least 50%. A stronger
tank is needed than for water because
the weight of a 50% caustic soda solu-
tion is around 1½ times the weight of
water or approximately 12¾ pounds
per gallon.
Curbings and Spills
As a safety measure in case of spills,
curbings should be erected around a
tank. These structures permit recovery
of spilled caustic liquor in some cases;
in others, they reduce the hazard of
disposing of spills. Regulations should
be checked to determine if there are
any containment requirements. When
most of a spill has been removed, the
rest should be cleaned up with lots of
water. Final traces of caustic soda can
be neutralized with dilute acid or sodi-
um bicarbonate solutions.
Do not dump caustic soda solution
into streams or waterways.
Disposal of caustic soda solution
should be done in accordance with
all applicable laws and regulations.
16 NaOH
CHAPTER 5
Caustic Soda Liquor
austic soda is a hazardous, obvious, the procedure would not be SPECIAL PRECAUTIONS

complete without them. A detailed
listing of steps is helpful from the
safety standpoint, too.
Storage tank inspection: Before con-
necting the tank car to the unloading
line, make sure the storage tank is
and should wear the recommended Placing Car for Unloading vented and the vent is open. Air dis-
protective clothing and equipment placed by the caustic soda solution
1. After the car is properly spotted, must be permitted to escape, other-
(see chapter 3). set handbrake and block wheels. wise the pressure could rupture a
This chapter describes the unloading 2. Caution signs must be so placed on tank. Also make sure there is room
of tank cars and the dilution of 73 per- the track of the car as to give nec- for the contents of the car so that
cent caustic soda solutions. essary warning to persons no caustic soda solution will over-
approaching the car from open end flow the tank.
When requested, PPG will assist com-
panies in evaluating and designing or ends of siding and must be left Lighting: During the hours of darkness
new unloading and handling systems up until after the car is unloaded no attempt should be made to connect
for bulk caustic soda in solution forms. and disconnected from discharge or disconnect a car or to open or close
connection. Signs must be of metal any attachment unless adequate light-
or other suitable material, at least ing is provided.
CAUSTIC SODA 12 by 15 inches in size and bear
SOLUTIONS the words “STOP—TANK CAR Do not enter cars under any circum-
Although the procedures described in CONNECTED,” the word “STOP” stances because of the possibility of
this section refer to unloading tank being in letters at least 4 inches caustic burns or suffocation due to
cars, the principles apply in general to high and the other words in letters insufficient oxygen.
tank trucks and barges. On request, at least 2 inches high. The letters
must be white on a blue back- Moving partially unloaded car: The
PPG will share information on proce- movement of partially unloaded cars
dures for unloading and handling, ground.
should be avoided. However, if it
since no two installations are alike. 3. Derails should be placed at the should be absolutely necessary to
Procedures for unloading 50 or 73 per- open end or ends of the siding move a partially unloaded tank car,
cent caustic soda solutions are the approximately one car length from make sure the outlet valve is closed
same up to the point where the flexi- the car being unloaded. and all connections to the car have
ble connection from the tank car ends. been disconnected. The manway
From there on they differ because the cover should be closed and all bolt
73 percent solution is usually diluted closures tightened securely. Unloading
before storage. lines should be drained.
Safety check: To prevent caustic
PREPARING TANK CARS soda from contacting personnel, make
FOR UNLOADING sure that all unloading connections,
NaOH
piping, joints, valves and storage tanks
The suggestions that follow are based
are sound and tight before unloading.
on procedures developed over the
After flow starts, check all around
years. While certain steps appear
Wheel chock Derail. Stop sign stands again for leaks.
for tank car. between tracks.
17
CHAPTER 5
Caustic Soda Liquor
out with compressed air to prevent

freezing. These channels should also
be left open to permit any condensate
still remaining after air-blowing to
drain out.
Wet or saturated steam at maximum
15 psig and 250°F must be used
because steam at higher tempera-
tures will damage the car lining and
may result in contamination of the
caustic liquor. Do not use superheat-
Preheating Liquid in Tank Car.
ed steam. Apply steam gradually to
prevent mechanical stresses. Heat
should never be applied to a car by
Sampling bottom. In fact, the bottom layer may
blowing steam into the caustic liquor.
have solidified even though the tem-
Since a sample is taken at the time of perature at the top is well above the Disconnect all steam lines as soon
loading, many users accept the ship- solution’s freezing point. as the proper unloading temperature
per’s analysis. However, on request,
has been obtained. No heat should
PPG will share information on proce- If a crust has formed on top of the
be applied during the actual unload-
dures for sampling tank car shipments. caustic soda solution, break it up
ing because the car lining will be
before heating the car contents so the
Preheating Liquid in Tank Car damaged.
solution can expand without exerting
All PPG tank cars are insulated so that dangerous pressure on the crust. You Thawing Frozen Bottom
caustic soda liquor is unlikely to can break it by inserting a U-tube Discharge Cock and Internal
freeze—but it may if the tank car through the manway onto the crust Valve at the Bottom of a Car
delivery is delayed. The 50% caustic and applying steam through the U-
tube. Never apply live steam directly The bottom discharge cock can be
soda solution is entirely fluid and can
onto the surface of caustic soda freed by steaming internally through
easily be unloaded when its tempera-
because of the danger of eruption. the valve opening or externally on the
ture is above 80°F.
surface of the cock.
The same goes for the 73% solution To apply steam to preheat the tank car
when its temperature is above 185°F. contents before unloading, attach a
Difficulty may be encountered in steam line to one of the connections.
attempting to unload at lower temper- Install a steam trap on the other con-
atures since viscosity is then greater nection (see diagram).
and there is a hazard of freezing in the The steam connections shown in the
unloading lines. Crystals start to form diagram on both sides of the dis-
NaOH
well above the freezing point. charge leg are for cars with heating
Also, caustic soda solution near the channels.
top of a tank car may be as much as In extremely cold weather, heating
20 degrees hotter than liquor near the channels should be drained and blown Testing internal
valve handle.
18
CHAPTER 5
Caustic Soda Liquor
If the internal valve cannot be opened

with reasonable pressure on the valve
handle, it indicates that caustic soda
around the valve is frozen and heat
should be applied to free it. Do not
attempt to force the valve by apply-
ing extreme pressure to the valve Above: Steam lance helps losen frozen valves.
handle as this may break the pin Right: Steam line should always be removed
connecting the valve to the valve prior to unloading.
rod and make bottom unloading
impossible.
The internal valve can be freed by
inserting a steam lance of ¼” copper
tubing up through the bottom dis-
charge cock and playing live steam
directly onto the internal valve. After a
period of 10 to 15 minutes, the frozen
caustic soda will have melted. Be sure
to withdraw lance and close bottom
discharge cock before again trying to
open internal valve. The internal valve
can now be opened.
Preheating
Unloading Lines
In cold weather it is good practice
to preheat unloading lines to prevent
cooling and solidifying of caustic soda
solutions at the start of unloading.
Preheating may be done by passing
steam directly through the line.
Sections of the unloading line exposed
to temperatures below 60°F should be
insulated.
19
CHAPTER 5
Caustic Soda Liquor
METHODS OF UNLOADING 5. Removing plug requires two

wrenches, one to remove plug and
Two methods are preferred for unload- one to hold valve so that it remains
ing tank cars: stationary. Caustic liquor that might
1. Through the bottom outlet valve have leaked through the internal
with a pump. valve and become caught between
the internal valve and bottom cock
2. Through the top by way of the could come out as a spray if the
eduction pipe with air pressure. bottom cock is not closed before
the plug is removed.
Unloading Through
Tank fittings at bottom of car.
Bottom Outlet Valve 6. Connect unloading line to the 2-inch
bottom cock. Top Unloading Through Eduction
1. Check the inside valve handle on
top of the car and make sure it is 7. See that all valves on the unloading
Pipe by Air Pressure
closed. If it is not, then the internal line are in the proper position for 1. Make sure the manway cover is
valve is not completely closed. unloading. securely fastened in place and all
Vibration in transit can loosen the nuts on the cover are tightened.
internal valve and permit caustic 8. Open the bottom cock.
liquor to leak by and become 2. Inspect all fittings at top of car for
9. Open internal valve. If this cannot
trapped above the bottom cock. defects before unloading to avoid
be done with reasonable pressure,
possible injury from caustic spray
2. Carefully open the one-inch cock on see earlier section entitled
after the car is put under air pres-
the air connection at the top of the “Thawing Frozen Bottom Discharge
sure.
car to release any pressure or vacu- Cock and Internal Valve…”.
um that might be in the car. Slicker 3. Every PPG car has a safety rupture
10. Start pump.
suit with face shield should be disc set at 165 pounds per square
worn. 11. After flow starts, check piping inch or a safety relief valve (SRV) at
valves and hose for leaks. 150 pounds per square inch. The air
3. Open the manway cover and sup- pressure should never exceed 75
port it in a partially open position 12. Check unloading progress from pounds per square inch (maximum).
during unloading. Underneath the time to time by looking into the Higher pressures may fracture the
manway cover handle are two eye- manway. rupture disc in the safety vent. If a
bolts which have the nuts mounted disc is ruptured while unloading, call
in such a way that they cannot be 13. When the car is empty, stop the
pump and close the internal valve. the PPG Industries Emergency
removed and the eyebolts cannot Response Center at (412) 434-4515
be swung out of the way until the Inspect the car through the man-
way to make sure it is empty. for further instructions.
cover has been lifted slightly. This
is a safety device to keep the cover 14. Prepare empty car for return (see 4. The air supply line should be
from being blown open. final section of this chapter for equipped with a pressure relief
NaOH
instructions). valve set at 75 pounds per square
4. On the manway cover nut-and-bolt inch (maximum); a pressure-reduc-
fastenings, use only end wrench- ing valve set at 70 pounds per
es—not pipe wrenches. square inch (maximum); a pressure
gage; and a shut-off valve.
20
CHAPTER 5
Caustic Soda Liquor
7. Connect the air supply line to the 1- tank cars at temperatures calculated
inch cock. This connection, which to arrive at 175 to 200°F. The hot con-
should also have flexibility, can be centrated solution is usually diluted to
made by using pressure hose or 50 percent and cooled before storage
flexible tubing. to reduce handling problems, embrit-
tlement of storage tanks, and iron
8. Apply air pressure slowly until there contamination from tanks.
is a normal flow of caustic liquor to
the storage tank. Use of minimum PPG Industries developed a system
air pressure is recommended. that has been used since 1939 for
unloading and diluting 73 percent
5. Remove the plug from the 1-inch air 9. If, after applying air pressure, no solution. Many years of service in
valve on top of the car. Open the caustic flows out of the car, contact numerous installations have shown
1-inch cock to relieve air pressure PPG Industries Customer Service. the system to be practical and eco-
or vacuum. Cup palm of rubber- nomical, and it must be supervised at
gloved hand over cock to prevent 10. Check fittings and line for leaks.
all times.
being sprayed. 11. Maintain the air pressure until the
tank car is completely empty. A As shown in the schematic diagram,
drop in the pressure and the sound the system discharges 73 percent
of air rushing through the dis- solution from the tank car to a centrifu-
Eduction pipe charge pipe tell you that the tank gal pump. Dilution water at constant
Air cock
car is empty. pressure is also fed to the suction side
of the pump. A rotameter indicates the
12. Shut off the air supply and 1-inch flow rate of dilution water. A valve con-
cock on the car. Disconnect the air trols the amount of water needed to
supply piping. Cupping your rub- give the 50 percent strength or any
ber-gloved hand for protection, other desired concentration.
open the 1-inch cock on the car to
make sure pressure has been Heat evolved by the diluting reaction
6. Check to see that the 2-inch cock released from the car before open- can raise the temperature of the dilut-
on top of the car is closed. Remove ing the manway cover. Then open ed 50 percent solution to as high as
the 2-inch plug and connect the the manway cover and inspect the 270°F. For safe storage in a steel tank,
eduction pipe to the unloading line car to make sure it is empty. solution temperature should be less
with a flexible hose. Open the cock. than 140°F. To cool the caustic liquor,
13. Prepare empty car for return it is pumped through a heat exchanger
Use of a flexible hose for connecting (see section on page 22 for before going to storage. The liquor
tank car to unloading line is recom- instructions). concentration can be determined by
mended. This will facilitate making simple measurements of specific grav-
connections and prevent a possible Unloading and Diluting 73
ity and temperature, and can be used
rupture of the line because the car Percent Caustic Liquor
NaOH
to control dilution.
rises during unloading as the weight
Since 73 percent caustic soda solution
on its springs decreases. This rise On request, PPG will share information
has a freezing point of approximately
may be as much as 6 inches. on planning and installing the dilution
145°F, it is shipped in lined, insulated
system.
21
CHAPTER 5
Caustic Soda Liquor
Preparing Empty Cars for Return Unloading Tank Trucks

1. Clean out unloading lines with Tank trucks are almost always
steam, water or air before discon- unloaded by the driver. Trailers are
necting. When disconnecting and equipped with 30 feet of hose unless
draining the unloading line, be care- additional hose is specified on the
ful not to spill caustic soda solution order. The hose is fitted with a
on personnel, the tank car or the two-inch quick-connect coupling.
ground. Wash off with water any The receiving installation should have
accidental spill on the car to mini- a two-inch quick-connect fitting on
mize damage to car and to protect the pipe to storage. This pipe should
trainmen who will be handling the be marked with a caustic soda
empty car. warning sign.
Hoses, valve and unloading connection at rear
of tank truck.
2. If steam line and steam trap were The trailer can be unloaded by air
used, remove them from car. In pressure from a compressor mounted
extremely cold weather, blow out on the truck. If a pump is needed on
car’s heating coils or channels with the truck for unloading, this should be
compressed air. specified on the order.
NaOH
3. Close all valves. Replace the The unloading area must have a
bottom outlet plug, or the eduction safety spray shower and eye-washing
pipe and air inlet plugs. Close and fountain for the driver’s protection.
tighten the manway cover and
valve housing cover at top of car.
22
CHAPTER 6
austic soda is a hazardous, cold water that is being stirred. If the Cleaning up Spills

water is not stirred, adding caustic
soda beads is dangerous and can
result in spattering and eruption. Don’t
and Disposing of Waste
When cleaning up a spill, wear proper
protective clothing and equipment.
safe handling practices and first aid, raise the concentration of caustic soda
and should wear the recommended by more than 5% with any single addi- Shovel up any spilled PELS caustic
protective clothing and equipment tion. Do not add caustic soda beads to soda beads. Do not put unneutralized
(see chapter 3). hot water. The water should be at waste caustic soda into a sewer or
ambient tempera- stream. Follow an approved procedure
ture. The high heat for neutralizing the spilled material and
of solution of dry getting rid of it in your waste disposal
caustic soda may system.
cause sudden evo- Flush the area contaminated by the
lution of steam and spill with huge quantities of water.
spattering and
eruption. Also a Waste material must be disposed of in
layer of concentrat- an approved hazardous waste facility.
ed solution may Care must be taken when using or dis-
Pressure differential rail car for delivery of PELS•caustic soda beads form and suddenly posing of chemical materials and/or
in bulk. mix with a layer of their containers to prevent environ-
BAGS AND DRUMS less concentrated mental contamination. Chemical
solution. In this case, the high heat of materials and/or their containers must
Take care to avoid breaking or punc- dilution may create steam and cause be disposed of in accordance with the
turing bags and drums of PELS caustic the solution to spatter and erupt. Clean Air Act, the Clean Water Act,
soda beads. Since anhydrous caustic the Resource Conservation and
soda left exposed to the atmosphere Disposing of Containers Recovery Act, as well as any other rel-
absorbs moisture and reacts with car- Flush all traces of PELS caustic soda evant federal, state, or local
bon dioxide, containers must be kept beads from drums. And then flush laws/regulations regarding disposal.
closed. The contents of broken bags or again to get rid of any dissolved caus- Do not re-use bag.
drums must be promptly used or tic soda adhering to the metal before
placed in suitable air-tight containers. Hazards
disposing of drums. This will protect
Drums and bags should be stored in a people handling these drums later on Avoid breathing dusts or mists from
dry place indoors. who may not recognize the traces as solutions.
Dissolving PELS beads: A short peri- being caustic soda or be aware of its
Avoid contact with acids, aluminum,
od of mechanical agitation is all that is dangers.
chromium, tin, zinc (galvanized metal),
needed to dissolve this form of caustic Disposing of Bags: Do not re-use bags. brass, bronze and organic materials.
soda in water completely. PELS beads Dispose of waste materials according to Such contact may generate explosive
dissolve twice as fast as flakes.
NaOH
approved procedures and regulatory or toxic materials. Avoid contact with
CAUTION: Do not add water to caus- laws/regulation regarding disposal. sugars. Such contact may generate
tic soda beads. The right way is to toxic carbon monoxide.
add the beads slowly to the surface of
23
CHAPTER 6
CSD (CLOSED SYSTEM Advantages of CSD Rail Car 5. ALL-WEATHER OPERATION:

DELIVERY) BULK System Rain and temperature extremes
U N LO A D I N G AND do not interfere with enclosed
HANDLING 1. HIGH SPEED: Unloading rate pneumatic conveying system;
ranges from 15 to 20 tons per hour. A do not stop unloading operations.
PPG engineers designed “CSD,” a 90-ton car can be unloaded in less
closed system delivery method for than an 8-hour shift. CSD operation
bulk shipping, handling and storing
PELS caustic soda. 2. REDUCED MANPOWER: One The diagram below shows the main
man can carry out the entire unloading components of a typical CSD closed
The company has a number of procedure. There is no need to unload loop pneumatic system.
pressure differential rail cars designed drums from boxcar or truck; move
for pneumatic unloading. Each has a them to storage area; and stack them. When conveying air is admitted to the
caustic soda compatible protective system, it passes over a desiccant to
coating. PPG also maintains its own 3. INCREASED SAFETY: Closed dry the air to a minimum dew point
fleet of lined pressure differential truck loop pneumatic conveying system temperature of –40° (measured at
trailers. helps reduce the opportunity for atmospheric pressure). The blower
human contact with caustic soda. compresses the air at a rate of 600
cubic feet per minute to 15 psig. Upon
4. IMPROVED HANDLING: When leaving the blower, the air is cooled in
exposed to the atmosphere, caustic a heat exchanger to a temperature
soda readily absorbs moisture. The less than 140°F. The air then enters a
crystals become soft and tacky so that manifold on the underside of the car
crusts and lumps can form in storage. through piping and flexible hose. The
By exposing caustic soda only to dry air is distributed from the manifold to
air in a closed loop system, CSD the car interior and to the conveying
avoids caking and retains the original line. When sufficient pressure has
free-flowing characteristics of anhy- built up in the car, a discharge valve is
Manifold piping of pressure differential rail car. drous caustic soda.
Automatic loading of piping of pressure

differential rail car.
CSD bulk unloading system for rail cars.

24
CHAPTER 6
opened. Anhydrous caustic soda can investment for a system to receive

now flow into the conveying line. The truck trailer shipments is less than one
caustic soda is carried through the designed for rail car deliveries.
conveying line by a high velocity air
stream to the top of the storage bin. CSD System Design
After the conveying air leaves the stor- Since anhydrous caustic soda is less
age bin, any entrained dust is removed corrosive than solutions, its demands
by an automatic self-cleaning bag-type upon materials of construction are less
filter. The filtered air is returned to the critical. Steel is the usual material. A
smooth, continuous surface inside the Dryer for closed system delivery is mounted
blower intake to complete the pneu- on trailer.
matic loop. Since the recycled air has
been in contact with highly hygro-
scopic caustic soda, this air is
extremely dry. Any make-up air that is
required enters the closed loop
through the air dryers at the blower
section. The air dryers reduce the dew
point of the make-up air to -40°F.
Between unloading operations, the Pressure differential hopper trailer for delivery
storage bin and other parts of the sys- conveying line and of PELS•caustic soda beads in bulk.
tem are protected against moisture a minimum of
pickup by the same dryers that admit bends promote
air to the system. The economical the efficiency
design plus the dual purpose of the of pneumatic
dryers is a unique feature of CSD. conveying.
Advantages of Each installation
CSD Truck Trailer System requires an
individual design
Trucks with hopper trailers deliver 22- dependent upon
ton shipments. These systems have existing plant
the same advantages just described facilities. On
for rail car systems plus additional request, PPG
benefits. will share
A blower is mounted on the truck and information
a dryer is mounted on the trailer (see in evaluating,
photo and diagram) so that the receiv- planning and
ing installation needs to include only a designing the
dust filter, a storage bin fitted with a complete system.
vent dryer and piping from the truck to
the storage bin. Accordingly, the
25 CSD bulk unloading system for truck trailers.
C H A P T E R 7
Technical Data
austic soda is a hazardous, carbon dioxide in the air to form Hydration

sodium carbonate. Conversion is
100 percent after prolonged exposure.
Therefore, minimum exposure to air is
Anhydrous caustic soda is a white
translucent solid with a fibrous crys-
talline structure. Being hygroscopic, it
safe handling practices and first aid, desirable in handling anhydrous forms.
and should wear the recommended On the other hand, the hygroscopic attracts water molecules and forms
protective clothing and equipment nature of anhydrous caustic soda hydrates. Six hydrates of caustic soda
(see chapter 3). makes it useful as a drying agent. have been identified, each with its
own distinctive crystalline structure.
Chemical Reactivity Solutions of caustic soda are strongly The number of water molecules
alkaline and have a high pH or high attached to each molecule of sodium
Caustic soda, either dry or in solution, concentration of negatively charged hydroxide, corresponding to the six
is not combustible; has no flash point, hydroxyl ions, OH-. The high reactivity hydrated forms, is 7, 5, 4, 3½, 2 or 1.
no autoignition temperature, and no of caustic soda with many organic and This degree of hydration depends upon
explosive limits. inorganic substances, including certain the temperature and concentration of
Anhydrous caustic soda is deliques- metals is the main reason for its the solution in which the crystals
cent (dissolving in moisture absorbed importance as a basic chemical. form, as shown in the diagram on the
from the atmosphere) and reacts with facing page. The curve shows the
freezing points of solutions with differ-
Anhydrous Sodium Hydroxide ent concentrations; the eutectic
Molecular Weight 40.005 solution is just less than 19 percent.
Melting Range 590 to 608°F (310 to 320°C)
Boiling Point 2534°F (1390°C)
Specific Gravity of Pure Solid
2.130
Refractive Index 1.3576
Heat of Fusion 72 Btu/lb
40.0 cal/g
Specific Heat at 20°C 0.48 Btu/(lb) (°F)
0.48 cal/(g) (°C)
Solubility in Water at 0°C 42 g/100 g water
At 100°C 347 g/100 g water
_____________________________________________________
Caustic Soda Solutions 50 Percent 73 Percent
Solution Solution
Melting Range
(crystallization begins) 41 to 51° F 140 to 143° F
(5 to 11° C) (60 to 62° C)
Solidification Point 41° F (5° C) 140° F (60° C)
26
C H A P T E R 7
Technical Data
27
C H A P T E R 7
Technical Data
Specific Gravity of Caustic Soda Solutions* At Various Temperatures
Percent 32°F 50°F 68°F 86°F 104°F 122°F 140°F 176°F 194°F 212°F
NaOH 0°C 10°C 20°C 30°C 40°C 50°C 60°C 80°C 90°C 100°C
2 1.024 1.023 1.021 1.018 1.014 1.010 1.004 0.993 0.987 0.980
4 1.048 1.046 1.043 1.039 1.035 1.031 1.025 1.014 1.008 1.001
6 1.071 1.068 1.065 1.061 1.056 1.052 1.046 1.035 1.028 1.022
8 1.094 1.091 1.087 1.083 1.078 1.073 1.068 1.056 1.050 1.043
10 1.117 1.113 1.109 1.014 1.100 1.094 1.089 1.077 1.071 1.064
12 1.140 1.136 1.131 1.126 1.121 1.116 1.110 1.098 1.092 1.086
14 1.162 1.158 1.153 1.148 1.143 1.137 1.132 1.120 1.113 1.107
16 1.185 1.180 1.175 1.170 1.165 1.159 1.153 1.141 1.134 1.128
18 1.207 1.202 1.197 1.192 1.186 1.181 1.175 1.162 1.156 1.149
20 1.230 1.224 1.219 1.214 1.208 1.202 1.196 1.183 1.177 1.170
22 1.252 1.247 1.241 1.235 1.230 1.224 1.217 1.205 1.198 1.191
24 1.274 1.269 1.263 1.257 1.251 1.245 1.239 1.226 1.219 1.212
26 1.295 1.291 1.285 1.279 1.273 1.267 1.260 1.247 1.241 1.234
28 1.318 1.312 1.306 1.300 1.294 1.288 1.281 1.268 1.262 1.255
30 …… 1.334 1.328 1.322 1.315 1.309 1.302 1.289 1.282 1.276
32 …… 1.355 1.349 1.343 1.336 1.330 1.323 1.310 1.303 1.296
34 …… …… 1.370 1.363 1.357 1.350 1.343 1.330 1.323 1.316
36 …… …… 1.390 1.384 1.377 1.370 1.363 1.350 1.343 1.336
38 …… …… 1.410 1.404 1.397 1.390 1.383 1.370 1.363 1.356
40 …… …… 1.430 1.423 1.416 1.410 1.403 1.389 1.382 1.375
42 …… …… 1.449 1.443 1.436 1.429 1.422 1.408 1.401 1.394
44 …… …… 1.468 1.462 1.455 1.448 1.441 1.427 1.420 1.413
46 …… …… 1.487 1.481 1.473 1.466 1.459 1.445 1.438 1.432
48 …… …… 1.506 1.500 1.492 1.485 1.478 1.464 1.457 1.450
50 …… …… 1.525 1.518 1.511 1.504 1.497 1.483 1.476 1.470
52 …… …… …… 1.537 1.530 1.524 1.517 1.503 1.496 1.490
54 …… …… …… …… 1.549 1.543 1.536 1.523 1.516 1.510
56 …… …… …… …… 1.568 1.562 1.556 1.543 1.536 1.530
58 …… …… …… …… …… 1.581 1.575 1.563 1.556 1.550
60 …… …… …… …… …… …… 1.597 1.583 1.576 1.570
62 …… …… …… …… …… …… …… 1.603 1.596 1.590
64 …… …… …… …… …… …… …… 1.623 1.616 1.610
66 …… …… …… …… …… …… …… 1.643 1.636 1.630
68 …… …… …… …… …… …… …… 1.663 1.656 1.650
70 …… …… …… …… …… …… …… 1.683 1.676 1.670
72 …… …… …… …… …… …… …… 1.703 1.696 1.690
74 …… …… …… …… …… …… …… 1.723 1.716 1.710
*These values are for pure sodium hydroxide in distilled water. Data below 50 percent were derived from “International Critical
28 Tables,” Volume III, page 79. Data above 50 percent were obtained by extrapolation.
C H A P T E R 7
Technical Data
29
C H A P T E R 7
Technical Data
Specific Gravity of Mercury Cell and Rayon Grade Caustic Soda Solutions* – In Range from 50.6 to 52.1%
Percent NaOH, 76% Na2O Basis (This is the billing basis described on page 8.)
°F 50.6 50.7 50.8 50.9 51.0 51.1 51.2 51.3 51.4 51.5 51.6 51.7 51.8 51.9 52.0 52.1
76 1.519 1.520 1.521 1.522 1.523 1.524 1.525 1.526 1.527 1.528 1.529 1.530 1.531 1.532 1.533 1.534
78 1.518 1.519 1.520 1.521 1.522 1.523 1.524 1.525 1.526 1.527 1.528 1.529 1.530 1.531 1.532 1.533
80 1.518 1.519 1.520 1.521 1.522 1.523 1.524 1.525 1.526 1.527 1.528 1.529 1.530 1.531 1.532 1.533
82 1.517 1.518 1.519 1.520 1.521 1.522 1.523 1.524 1.525 1.526 1.527 1.528 1.529 1.530 1.531 1.532
84 1.516 1.517 1.518 1.519 1.520 1.521 1.522 1.523 1.524 1.525 1.526 1.527 1.528 1.529 1.530 1.531
86 1.515 1.516 1.517 1.518 1.519 1.520 1.521 1.522 1.523 1.524 1.525 1.526 1.527 1.528 1.529 1.530
88 1.514 1.515 1.516 1.517 1.518 1.519 1.520 1.521 1.522 1.523 1.524 1.525 1.526 1.527 1.528 1.529
90 1.514 1.515 1.516 1.516 1.517 1.518 1.520 1.520 1.521 1.522 1.523 1.524 1.526 1.527 1.527 1.528
92 1.513 1.514 1.515 1.516 1.517 1.518 1.519 1.520 1.521 1.522 1.523 1.524 1.525 1.526 1.527 1.528
94 1.512 1.513 1.514 1.515 1.516 1.517 1.518 1.519 1.520 1.521 1.522 1.523 1.524 1.525 1.526 1.527
98 1.510 1.511 1.512 1.513 1.514 1.515 1.516 1.517 1.518 1.519 1.520 1.521 1.522 1.523 1.524 1.525
100 1.509 1.510 1.511 1.512 1.513 1.514 1.515 1.516 1.517 1.518 1.519 1.520 1.521 1.522 1.523 1.524
102 1.509 1.510 1.511 1.512 1.512 1.514 1.515 1.516 1.516 1.517 1.519 1.520 1.520 1.521 1.522 1.523
104 1.508 1.509 1.510 1.511 1.512 1.513 1.514 1.515 1.516 1.517 1.518 1.519 1.520 1.521 1.522 1.523
106 1.507 1.508 1.509 1.510 1.511 1.512 1.513 1.514 1.515 1.516 1.517 1.518 1.519 1.520 1.521 1.522
108 1.506 1.507 1.508 1.509 1.510 1.511 1.512 1.513 1.514 1.515 1.516 1.517 1.518 1.519 1.520 1.521
110 1.505 1.506 1.507 1.508 1.509 1.510 1.511 1.512 1.513 1.514 1.515 1.516 1.517 1.518 1.519 1.520
112 1.504 1.505 1.506 1.507 1.508 1.509 1.510 1.511 1.512 1.513 1.514 1.515 1.516 1.517 1.518 1.519
114 1.504 1.505 1.506 1.507 1.507 1.508 1.510 1.511 1.511 1.512 1.513 1.514 1.515 1.516 1.517 1.518
116 1.503 1.504 1.505 1.506 1.507 1.508 1.509 1.510 1.511 1.512 1.513 1.514 1.515 1.516 1.517 1.518
118 1.502 1.503 1.504 1.505 1.506 1.507 1.508 1.509 1.510 1.511 1.512 1.513 1.514 1.515 1.516 1.517
120 1.501 1.502 1.503 1.504 1.505 1.506 1.507 1.508 1.509 1.510 1.511 1.512 1.513 1.514 1.515 1.516
122 1.500 1.501 1.502 1.503 1.504 1.505 1.506 1.507 1.508 1.509 1.510 1.511 1.512 1.513 1.514 1.515
124 1.500 1.500 1.502 1.502 1.503 1.504 1.505 1.506 1.507 1.508 1.509 1.510 1.511 1.512 1.513 1.514
126 1.499 1.500 1.501 1.502 1.503 1.504 1.505 1.506 1.507 1.507 1.509 1.510 1.511 1.512 1.513 1.514
128 1.498 1.499 1.500 1.501 1.502 1.503 1.504 1.505 1.506 1.507 1.508 1.509 1.510 1.511 .1512 1.513
130 1.497 1.498 1.499 1.500 1.501 1.502 1.503 1.504 1.505 1.506 1.507 1.508 1.509 1.510 1.511 1.512
132 1.496 1.497 1.498 1.499 1.500 1.501 1.502 .1503 1.504 1.505 1.506 1.507 1.508 1.509 1.510 1.511
134 1.495 1.496 1.497 1.498 1.499 1.500 1.501 1.502 1.503 1.504 1.505 1.506 1.507 1.508 1.509 1.510
136 1.495 1.495 1.497 1.498 1.499 1.500 1.500 1.502 1.502 1.503 1.505 1.505 1.506 1.507 1.508 1.509
138 1.494 1.495 1.496 1.497 1.498 1.499 1.500 1.501 1.502 1.503 1.504 1.505 1.506 1.507 1.507 1.508
140 1.493 1.494 1.495 1.496 1.497 1.498 1.499 1.500 1.501 1.502 1.503 1.504 1.505 1.506 1.507 1.508
*The specific gravity values in this table do not correlate with those on page 27, which are based on pure sodium hydroxide in distilled water. In contrast, the values on this page are on a 76 per-
cent Na2O basis, which includes sodium carbonate, as explained in detail on page 8. Furthermore, the standard and low-iron grade caustic soda solutions contain over two percent sodium chloride
NaOH
on a 100% NaOH basis.
Note: Table data based on water at 39.2°F (4°C).
30
C H A P T E R 7
Technical Data
Specific Gravity of Standard and Low-Iron Grade Caustic Soda Solutions* – In Range from 50.6 to 52.1%
Percent NaOH, 76% Na2O Basis (This is the billing basis described on page 11.)
°F 50.6 50.7 50.8 50.9 51.0 51.1 51.2 51.3 51.4 51.5 51.6 51.7 51.8 51.9 52.0 52.1
76 1.526 1.527 1.529 1.530 1.531 1.532 1.533 1.534 1.535 1.536 1.537 1.537 1.538 1.539 1.540 1.541
78 1.525 1.527 1.528 1.529 1.531 1.532 1.532 1.533 1.534 1.535 1.536 1.537 1.538 1.539 1.540 1.541
80 1.525 1.526 1.527 1.529 1.530 1.531 1.531 1.533 1.534 1.534 1.535 1.536 1.537 1.538 1.539 1.540
82 1.524 1.525 1.527 1.528 1.529 1.530 1.531 1.532 1.533 1.534 1.534 1535 1.536 1.537 1.538 1.539
84 1.523 1.524 1.526 1.527 1.528 1.529 1.530 1.531 1.532 1.533 1.533 1.534 1.535 1.536 1.537 1.538
86 1.522 1.524 1.525 1.526 1.528 1.529 1.529 1.530 1.531 1.532 1.533 1.534 1.535 1.536 1.537 1.537
88 1.522 1.523 1.524 1.525 1.527 1.528 1.528 1.530 1.530 1.531 1.532 1.533 1.534 1.535 1.536 1.537
90 1.521 1.522 1.523 1.525 1.526 1.527 1.528 1.529 1.530 1.530 1.531 1.532 1.533 1.534 1.535 1.536
92 1.520 1.521 1.523 1.524 1.525 1.526 1.527 1.528 1.529 1.530 1.530 1.531 1.532 1.533 1.534 1.535
94 1.519 1.521 1.522 1.523 1.524 1.525 1.526 1.527 1.528 1.529 1.530 1.531 1.532 1.533 1.534 1.534
96 1.518 1.520 1.521 1.522 1.524 1.525 1.525 1.526 1.527 1.528 1.529 1.530 1.531 1.532 1.533 1.534
98 1.518 1.519 1.520 1.522 1.523 1.524 1.525 1.526 1.527 1.527 1.528 1.529 1.530 1.531 1.532 1.533
100 1.517 1.518 1.520 1.521 1.522 1.523 1.524 1.525 1.526 1.527 1.527 1.528 1.529 1.530 1.531 1.532
102 1.516 1.517 1.519 1.20 1.521 1.522 1.523 1.524 1.525 1.526 1.527 1.528 1.529 1.530 1.530 1.531
104 1.515 1.517 1.518 1.519 1.521 1.522 1.522 1.523 1.524 1.525 1.526 1.527 1.528 1.529 1.530 1.531
106 1.515 1.516 1.517 1.519 1.520 1.521 1.521 1.522 1.523 1.524 1.525 1.526 1.527 1.528 1.529 1.530
108 1.514 1.515 1.516 1.518 1.519 1.520 1.521 1.522 1.523 1.523 1.524 1.525 1.526 1.527 1.528 1.529
110 1.513 1.514 1.516 1.517 1.518 1.519 1.520 1.521 1.522 1.523 1.523 1.524 1.525 1.526 1.527 1.528
112 1.512 1.514 1.515 1.516 1.517 1.518 1.519 1.520 1.521 1.522 1.523 1.524 1.524 1.526 1.527 1.527
114 1.511 1.513 1.514 1.515 1.517 1.518 1.518 1.519 1.520 1.521 1.522 1.523 1.524 1.525 1.526 1.527
116 1.511 1.512 1.513 1.515 1.516 1.517 1.518 1.519 1.519 1.520 1.521 1.522 1.523 1.524 1.525 1.526
118 1.510 1.511 1.513 1.514 1.515 1.516 1.517 1.518 1.519 1.520 1.520 1.521 1.522 1.523 1.524 1.525
120 1.509 1.510 1.512 1.513 1.514 1.515 1.516 1.517 1.518 1.519 1.520 1.520 1.521 1.522 1.523 1.524
122 1.508 1.510 1.511 1.512 1.514 1.515 1.515 1.516 1.517 1.518 1.519 .1520 1.521 1.522 1.523 1.524
124 1.508 1.509 1.510 1.512 1.513 1.514 1.514 1.515 1.516 1.517 1.518 1.519 1.520 1.521 1.522 1.523
126 1.507 1.508 1.510 1.511 .1512 1.513 1.514 1.515 1.515 1.516 1.517 1.518 1.519 1.520 1.521 1.522
128 1.506 1.507 1.509 1.510 1.511 1.512 1.513 1.514 1.515 1.516 1.516 1.517 1.518 1.519 1.520 1.521
130 1.505 1.507 1.508 1.509 1.510 1.511 1.512 1.513 .1514 1.515 1.516 1.517 1.518 1.519 1.520 1.520
132 1.504 1.506 1.507 1.508 1.510 1.511 1.511 1.512 1.513 1.514 1.515 1.516 1.517 1.518 1.519 1.520
134 1.504 1.515 1.506 1.508 1.509 1.510 1.511 1.511 1.512 1.513 1.514 1.515 1.516 1.517 1.518 1.519
136 1.503 1.504 1.506 1.507 1.508 1.509 1.510 1.511 1.511 1.512 1.513 1.514 1.515 1.516 1.517 1.518
138 1.502 1.503 1.505 1.506 1.507 1.508 1.509 1.510 1.511 1.512 1.513 1.513 1.514 1.515 1.517 1.517
140 1.501 1.503 1.504 1.505 1.506 1.507 1.508 1.509 1.510 1.511 1.512 1.513 1.514 1.515 1.516 1.517
*The specific gravity values in this table do not correlate with those on page 27, which are based on pure sodium hydroxide in distilled water. In contrast, the values on this page
NaOH
are on a 76 percent Na2O basis, which includes sodium carbonate, as explained in detail on page 8. Furthermore, the standard and low-iron grade caustic soda solutions contain
over two percent sodium chloride on a 100% NaOH basis.
Note: Table data based on water at 39.2°F (4°C).
31
C H A P T E R 7
Technical Data
Density of Caustic Soda Solutions at 60 Degrees Fahrenheit
American Pounds NaOH Pounds of Solution
Specific Standard Grams
Percent Percent Gravity Baumé Degrees NaOH Per Per Per Per
NaOH Na2O 60/60°F Degrees Twaddell Per Liter Gallon Cubic Foot Gallon Cubic Foot
2 1.55 1.023 3.26 4.6 21 1.17 1.28 8.53 63.80

4 3.10 1.045 6.24 9.0 42 0.35 2.60 8.71 65.18
6 4.65 1.067 9.10 13.4 64 0.53 3.99 8.90 66.55
8 6.20 1.090 11.97 18.0 87 0.73 5.44 9.09 67.98
10 7.75 1.112 14.60 22.4 111 0.93 6.94 9.27 69.36
12 9.30 1.134 18.13 26.8 136 1.13 8.49 9.45 70.74
14 10.85 1.156 19.57 31.2 162 1.35 10.09 9.63 72.10
16 12.40 1.178 21.91 35.6 188 1.57 11.76 9.82 73.47
18 13.95 1.201 23.27 40.2 215 1.80 13.44 10.01 74.91
20 15.50 1.223 26.44 44.6 244 2.04 15.26 10.20 76.28
22 17.05 1.245 28.53 49.0 274 2.28 17.08 10.38 77.65
24 18.60 1.267 30.66 53.4 304 2.53 18.96 10.56 79.02
26 20.15 1.289 32.51 57.8 335 2.79 20.90 10.75 80.39
28 21.70 1.310 34.31 62.0 366 3.06 22.88 10.92 81.70
30 23.25 1.332 36.14 66.4 399 3.33 24.92 11.11 83.08
32 24.80 1.353 37.83 70.6 433 3.61 27.00 11.28 84.39
34 26.35 1.374 39.47 74.8 467 3.89 29.14 11.46 85.71
36 27.90 1.394 40.98 78.8 501 4.18 31.30 11.62 86.95
38 29.45 1.415 42.53 83.0 537 4.48 33.53 11.80 88.25
40 31.00 1.434 43.88 86.8 573 4.78 35.78 11.96 89.45
42 32.55 1.454 45.28 90.8 610 5.09 38.09 12.12 90.70
44 34.10 1.473 46.66 94.6 648 5.40 40.42 12.28 91.87
46 35.65 1.492 47.82 98.4 686 5.72 42.81 12.44 93.06
48 37.20 1.511 49.04 102.2 725 6.04 45.24 12.60 94.24
50 38.75 1.530 50.23 106.0 754 6.38 47.72 12.76 95.43
52 40.30 1.549 51.39 109.8 805 6.71 50.24 12.92 96.62
32 NaOH
C H A P T E R 7
Technical Data
Density of Caustic Soda Solutions at 212 Degrees Fahrenheit
American Pounds NaOH Pounds of Solution
Specific Standard Grams
Percent Percent Gravity Baumé Degrees NaOH Per Per Per Per
NaOH Na2O 212/60°F Degrees Twaddell Per Liter Gallon Cubic Foot Gallon Cubic Foot
52 40.30 1.49 47.68 98 774 6.46 48.32 12.42 92.93

54 41.85 1.51 48.97 102 815 6.80 50.86 12.59 94.18
56 43.40 1.53 50.23 106 856 7.15 53.44 12.76 95.43
58 44.95 1.55 51.45 110 898 7.49 56.07 12.92 96.67
60 46.50 1.57 52.64 114 941 7.85 58.75 13.09 97.92
62 48.05 1.59 53.81 118 985 8.22 61.49 13.26 99.17
64 49.60 1.61 54.94 122 1030 8.59 64.27 13.42 100.42

66 51.15 1.63 56.04 126 1075 8.97 67.10 13.59 101.66
68 52.70 1.65 57.12 130 1121 9.36 69.98 13.76 102.91
70 54.25 1.67 58.17 134 1168 9.74 72.91 13.92 104.16
72 55.80 1.69 59.20 138 1216 10.14 75.90 14.09 105.41
74 57.35 1.71 60.20 142 1264 10.55 78.92 14.26 106.65
33 NaOH
C H A P T E R 7
Technical Data
34
C H A P T E R 7
Technical Data
Viscosity of Caustic Soda Solutions
Viscosity, centipoises
Percent 68°F 86°F 104°F 122°F 140°F 158°F
NaOH 20°C 30°C 40°C 50°C 60°C 70°C
2 1.10 0.90 0.72 0.62 0.52 0.44

4 1.28 1.02 0.82 0.69 0.59 0.49
6 1.48 1.18 0.94 0.77 0.66 0.55
8 1.69 1.32 1.07 0.88 0.74 0.62
10 1.92 1.50 1.21 0.99 0.83 0.70
12 2.2 1.7 1.4 1.1 0.9 0.8
14 2.7 2.0 1.6 1.3 1.0 0.9
16 3.2 2.3 1.8 1.5 1.2 1.0
18 3.8 2.7 2.1 1.7 1.4 1.2
20 4.4 3.3 2.3 2.0 1.6 1.3
22 5.6 3.9 2.8 2.3 1.9 1.5
24 7.0 4.6 3.3 2.7 2.1 1.8
26 8.8 5.6 4.0 3.2 2.5 2.0
28 11.0 6.8 4.9 3.7 2.8 2.3
30 13.4 8.6 5.9 4.4 3.2 2.6
32 17.0 10.3 7.0 5.0 3.7 2.9
34 20.6 12.6 8.2 5.8 4.2 3.3
36 25.5 14.5 9.8 6.7 4.7 3.7
38 31.0 17.3 11.2 7.5 5.4 4.1
40 36.0 20.3 12.6 8.4 6.0 4.5
42 44.0 23.5 14.7 9.8 6.6 5.0
44 52.0 27.0 16.5 10.6 7.4 5.5
46 60.0 31.0 18.5 11.8 8.2 6.0
48 70.0 35.0 20.2 13.0 9.0 6.5
50 78.3 39.5 22.1 14.0 9.7 7.1
35 NaOH
C H A P T E R 7
Technical Data
36
C H A P T E R 7
Technical Data
37
C H A P T E R 7
Technical Data
Specific Heat of Caustic Soda Solutions
Percent Specific Heat, Btu per Pound per Degree Fahrenheit
NaOH 32°F 40°F 50°F 60°F 80°F 100°F 120°F 140°F 160°F 180°F 200°F 220°F 240°F 260°F 280°F 300°F
0 1.004 1.003 1.001 0.999 0.998 0.997 0.998 0.999 1.000 1.002 1.004 ......... ......... ......... ......... .........
2 0.965 0.967 0.968 0.969 0.972 0.974 0.977 0.978 0.980 0.983 0.986 ......... ......... ......... ......... .........
4 0.936 0.940 0.943 0.946 0.951 0.954 0.957 0.960 0.962 0.965 0.966 ......... ......... ......... ......... .........
6 0.914 0.920 0.924 0.928 0.933 0.938 0.941 0.944 0.946 0.948 0.950 ......... ......... ......... ......... .........
8 0.897 0.902 0.907 0.911 0.918 0.923 0.927 0.930 0.932 0.934 0.936 ......... ......... ......... ......... .........
10 0.882 0.888 0.893 0.897 0.905 0.911 0.916 0.918 0.920 0.922 0.923 ......... ......... ......... ......... .........
12 0.870 0.877 0.883 0.887 0.894 0.901 0.906 0.909 0.911 0.912 0.913 ......... ......... ......... ......... .........
14 0.861 0.868 0.874 0.879 0.886 0.892 0.897 0.901 0.903 0.903 0.904 ......... ......... ......... ......... .........
16 0.853 0.860 0.866 0.871 0.880 0.886 0.891 0.894 0.896 0.897 0.897 ......... ......... ......... ......... .........
18 0.847 0.854 0.860 0.865 0.873 0.880 0.885 0.888 0.890 0.891 0.891 ......... ......... ......... ......... .........
20 0.842 0.848 0.854 0.859 0.868 0.875 0.880 0.884 0.886 0.886 0.887 ......... ......... ......... ......... .........
22 0.837 0.844 0.849 0.854 0.863 0.870 0.876 0.880 0.882 0.882 0.883 ......... ......... ......... ......... .........
24 ......... 0.839 0.844 0.849 0.858 0.866 0.873 0.877 0.879 0.879 0.880 ......... ......... ......... ......... .........
26 ......... 0.835 0.840 0.845 0.854 0.863 0.869 0.874 0.875 0.876 0.876 ......... ......... ......... ......... .........
28 ......... 0.830 0.836 0.841 0.850 0.859 0.866 0.870 0.872 0.872 0.873 ......... ......... ......... ......... .........
30 ......... 0.826 0.832 0.837 0.846 0.855 0.862 0.866 0.868 0.869 0.869 ......... ......... ......... ......... .........
32 ......... 0.822 0.828 0.833 0.842 0.850 0.857 0.862 0.863 0.864 0.864 ......... ......... ......... ......... .........
34 ......... ......... 0.823 0.828 0.837 0.845 0.852 0.856 0.857 0.858 0.858 ......... ......... ......... ......... .........
36 ......... ......... 0.819 0.824 0.832 0.840 0.845 0.849 0.850 0.851 0.851 ......... ......... ......... ......... .........
38 ......... ......... 0.816 0.820 0.827 0.833 0.837 0.841 0.842 0.842 0.843 ......... ......... ......... ......... .........
40 ......... ......... 0.812 0.815 0.821 0.826 0.829 0.831 0.832 0.832 0.832 ......... ......... ......... ......... .........
42 ......... ......... 0.807 0.809 0.813 0.816 0.819 0.819 0.820 0.820 0.820 ......... ......... ......... ......... .........
44 ......... ......... ......... 0.802 0.804 0.806 0.807 0.807 0.807 0.806 0.804 ......... ......... ......... ......... .........
46 ......... ......... ......... 0.793 0.794 0.795 0.794 0.794 0.793 0.791 0.789 ......... ......... ......... ......... .........
48 ......... ......... ......... ......... 0.783 0.782 0.781 0.780 0.779 0.777 0.776 ......... ......... ......... ......... .........
50 ......... ......... ......... ......... 0.771 0.769 0.768 0.767 0.765 0.765 0.764 0.763 0.762 0.762 0.761 0.761
52 ......... ......... ......... ......... 0.759 0.757 0.756 0.754 0.753 0.752 0.751 0.749 0.748 0.747 0.746 0.745
54 ......... ......... ......... ......... 0.746 0.744 0.741 0.739 0.739 0.738 0.737 0.735 0.733 0.731 0.730 0.728
56 ......... ......... ......... ......... 0.733 0.730 0.728 0.726 0.724 0.723 0.722 0.721 0.719 0.717 0.715 0.713
58 ......... ......... ......... ......... ......... 0.719 0.717 0.715 0.713 0.711 0.709 0.707 0.705 0.703 0.702 0.700
60 ......... ......... ......... ......... ......... 0.706 0.705 0.703 0.701 0.699 0.697 0.695 0.693 0.691 0.690 0.688
62 ......... ......... ......... ......... ......... ......... 0.694 0.692 0.690 0.688 0.687 0.685 0.683 0.681 0.679 0.677
64 ......... ......... ......... ......... ......... ......... 0.684 0.682 0.681 0.679 0.677 0.675 0.673 0.671 0.670 0.668
66 ......... ......... ......... ......... ......... ......... 0.675 0.673 0.671 0.669 0.668 0.666 0.664 0.662 0.660 0.658
68 ......... ......... ......... ......... ......... ......... ......... 0.663 0.662 0.660 0.658 0.656 0.655 0.653 0.651 0.649
70 ......... ......... ......... ......... ......... ......... ......... 0.655 0.653 0.651 0.649 0.647 0.646 0.644 0.642 0.640
72 ......... ......... ......... ......... ......... ......... ......... ......... 0.645 0.643 0.641 0.639 0.637 0.635 0.634 0.632
74 ......... ......... ......... ......... ......... ......... ......... ......... ......... 0.635 0.633 0.631 0.629 0.628 0.626 0.624
76 ......... ......... ......... ......... ......... ......... ......... ......... ......... 0.628 0.627 0.625 0.623 0.621 0.619 0.617
78 ......... ......... ......... ......... ......... ......... ......... ......... ......... ......... 0.620 0.618 0.616 0.615 0.613 0.611
Derived from data of Bertetti and McCabe, “Industrial Engineering Chemistry,” Volume 28, page 378, and McCabe and Wilson, “Industrial Engineering Chemistry,” Volume 34,
38 page 558.
C H A P T E R 7
Technical Data
HOW TO USE HEAT SOLUTION:
CONTENT (ENTHALPY)
CHART The relative heat contents of a 50 per- respectively. The difference between
cent caustic soda solution at 263°F these heat content values, 100 Btu per
Use of the chart on the facing page and at 120°F appear on the chart at pound of solution, is the answer.
simplifies the calculation of many the 272 and 162 heat content lines
problems frequently encountered in
diluting, cooling or heating caustic
soda solutions such as:
1. How to determine the temperature
of the final solution resulting from
the dilution of a caustic soda solu-
tion, assuming no heat loss.
2. How to determine the amount of heat
to remove from or add to a caustic
soda solution to change its tempera-
ture a desired number of degrees.
Examples
PROBLEM 1:
What will be the temperature of a 50
percent caustic soda solution prepared
by diluting a 73 percent solution at
200°F with water at 80°F?
SOLUTION:
Draw a straight line between these two
points on the chart: (1) the intersection
of the 73 percent caustic soda line and
the 200°F curve, and (2) the intersec-
tion of the 0 percent caustic soda line
and the 80°F curve. The line drawn
crosses the 50 percent caustic soda
line at 263°F, which is the answer.
PROBLEM 2:
How many Btu per pound of solution
must be removed to cool a 50 percent
caustic soda solution from 263°F to
120°F?
39
C H A P T E R 7
Technical Data
40
C H A P T E R 7
Technical Data
41
C H A P T E R 7
Technical Data
42
C H A P T E R 7
Technical Data
HOW TO USE CHART Examples drawn line intersects the 19 percent
FOR DILUTING AND vertical line, read 70 gallons of weak
MIXING CAUSTIC SODA PROBLEM 1 (a): solution needed at right and 30 gallons
SOLUTIONS How many gallons of water should be of strong solution needed at left.
Use of the chart on the facing page added to dilute 16,000 gallons of 73 Multiply the percentage ratio,
simplifies the calculation of problems percent caustic soda solution to 50
such as: percent? 70 gallons weak solution
30 gallons strong solution
1. How much water is needed to SOLUTION:
dilute a strong caustic soda solu- Draw a line from zero percent on the x 1,000 gallons strong solution
tion to a weaker one? weak solution scale at top to 73 per- = 2,333 gallons weak solution
2. How many gallons of strong solu- cent on the strong solution scale at The answer is the number of gallons
tion are needed to bring a weak bottom. From the point where the of water to be added.
solution to a higher concentration? drawn line intersects the 50 percent
vertical line, read 44 gallons of weak PROBLEM 2:
3. What is the strength of a solution solution needed at right and 56 gallons
How many gallons of 50 percent caus-
formed by mixing equal volumes of of strong solution needed at left.
tic soda solution should be added to
water and a caustic soda solution?
Multiply the percentage ratio, 300 gallons of 10 percent solution to
The left-hand line of the chart, zero obtain a final solution of 18 percent
percent, is of course water. The 44 gallons weak solution concentration?
decreasing heights from left to right of 56 gallons strong solution
the vertical lines for percentage con-
SOLUTION:
centration reflect the greater weight x 16,000 gallons strong solution
Draw a line from 10 percent on the
per gallon of stronger solutions. The = 12,571 gallons weak solution
weak solution scale at top to 50 per-
chart does not take into consideration The answer is the number of gallons cent on the strong solution scale at
differences in initial temperatures of of water to be added. bottom. From the point where the
solutions and water as well as volu- drawn line intersects the 18 percent
metric changes caused by heat of PROBLEM 1 (b): vertical line, read 84 gallons of weak
dilution since these conditions usually solution needed at right and 16 gallons
How many gallons of water should be
have relatively small effects on final of strong solution needed at left.
added to dilute 1,000 gallons of 50
volume.
percent caustic soda solution to 19 Multiply the percentage ratio,
percent? (The latter concentration has
the lowest freezing point and can 16 gallons weak solution
withstand storage temperatures down 84 gallons strong solution
to approximately -18°F.)
x 300 gallons weak solution
SOLUTION: = 57 gallons strong solution
NaOH
Draw a line from zero percent on the The answer is the number of gallons
weak solution scale at top to 50 per- of 50 percent caustic soda solution to
cent on the strong solution scale at be added.
bottom. From the point where the
43
C H A P T E R 7
Technical Data
PROBLEM 3: SOLUTION:
sents the 50:50 percentage ratio of
What is the strength of the solution Draw a line from zero percent on the the 10,000-gallon volumes stated in
formed by mixing 10,000 gallons of 40 weak solution scale at top to 40 per- the problem. The drawn line intersects
percent caustic soda solution with cent on the strong solution scale at the horizontal ratio line at the 23 per-
10,000 gallons of water? bottom. The horizontal line connecting cent vertical line, which is the
50 on both left and right scales repre- concentration of the final solution.
44
C H A P T E R 7
Technical Data
Alkali Conversion Tables
Equivalence of Sodium Oxide ( Na2O), Caustic Soda (NaOH) and Soda Ash (Na2CO3)
Na2O NaOH Na2CO3 Na2O NaOH Na2CO3 Na2O NaOH Na2CO3 Na2O NaOH Na2CO3
1 1.2906 1.7099 21 27.10 35.91 41 52.91 70.11 61 78.73 104.30
2 2.58 3.42 22 28.39 37.62 42 54.20 71.82 63 81.31 106.01
3 3.87 5.13 23 29.68 39.33 43 55.50 73.53 63 81.31 107.72
4 5.16 6.84 24 30.97 41.04 44 56.79 75.24 64 82.60 109.43
5 6.45 8.55 25 32.26 42.75 45 58.08 76.94 65 83.89 111.14
6 7.74 10.26 26 33.56 44.46 46 59.37 78.65 55 84.18 112.85
7 9.03 11.97 27 34.85 46.17 47 60.66 80.36 67 86.47 114.56
8 10.32 13.68 28 36.14 47.88 48 61.95 82.07 68 87.76 116.27
9 11.61 15.39 29 37.43 49.59 49 63.24 83.78 59 89.05 117.98
10 12.90 17.10 30 38.72 51.30 50 64.53 85.49 70 90.34 119.69
11 14.20 18.81 31 40.01 53.01 51 65.82 87.20 71 91.63 121.40
12 15.49 20.52 32 41.30 54.72 52 67.11 88.91 72 92.92 123.11
13 16.78 22.23 33 42.59 56.43 53 68.40 90.62 73 94.21 124.82
14 18.07 23.94 34 42.88 58.14 54 69.69 92.33 74 95.50 126.53
15 19.36 25.65 35 45.17 59.85 55 70.98 94.04 75 96.79 128.24
16 20.65 27.36 36 46.46 61.56 56 72.27 95.75 76 98.08 129.95
17 21.94 29.07 37 47.75 63.27 57 73.56 97.46 77 99.38 131.66
18 23.23 30.78 38 49.04 64.98 58 74.85 99.17 77.48 100 132.49
19 24.52 32.49 39 50.33 66.69 59 76.14 100.88
20 25.81 34.20 40 51.62 68.40 60 77.44 102.59
NaOH Na2O Na2CO3 NaOH Na2O Na2CO3 NaOH Na2O Na2CO3 NaOH Na2O Na2CO3
1 .7748 1.3249 26 20.15 34.45 51 39.52 67.57 76 58.88 100.69
2 1.55 2.65 27 20.92 35.77 52 40.29 68.89 77 59.66 102.02
3 2.32 3.97 28 21.69 37.10 53 41.07 70.22 78 60.44 103.34
4 3.10 5.30 29 22.47 38.42 54 41.84 71.54 79 61.21 104.67
5 3.87 6.62 30 23.24 39.75 55 42.62 72.87 80 61.98 105.99
6 4.65 7.95 31 24.02 41.07 56 43.39 74.19 81 62.76 107.32
7 5.42 9.27 32 24.79 42.40 57 44.16 75.52 82 63.53 108.64
8 6.20 10.60 33 25.57 43.72 58 44.94 76.84 83 64.31 109.97
9 6.97 11.92 34 26.34 45.05 59 45.71 78.17 84 65.08 111.29
10 7.75 13.25 35 27.12 46.37 60 46.49 79.49 85 65.86 112.62
11 8.52 14.57 36 27.89 47.70 61 47.26 80.82 86 66.63 113.94
12 9.30 15.90 37 28.67 49.02 62 48.04 82.14 87 67.41 115.27
13 10.07 17.22 38 29.44 50.35 63 48.81 83.47 88 68.18 116.59
14 10.85 18.55 39 30.22 51.67 64 49.59 84.79 89 68.95 117.92
15 11.62 19.87 40 30.99 53.00 65 50.36 86.12 90 69.73 119.24
16 12.40 21.20 41 31.77 54.32 66 51.14 87.44 91 70.51 120.57
17 13.17 22.52 42 32.54 55.65 67 51.91 88.77 92 71.28 121.89
18 13.95 23.85 43 33.32 56.97 68 52.69 90.09 93 72.06 123.22
19 14.72 25.17 44 34.09 58.29 69 53.46 91.42 94 72.83 124.54
20 15.50 26.50 45 34.87 59.62 70 54.24 92.74 95 73.61 125.87
21 16.27 27.82 46 35.64 60.94 71 55.01 94.07 96 74.38 127.19
22 17.05 29.14 47 36.42 62.27 72 55.79 95.39 97 75.16 128.52
23 17.82 30.47 48 37.19 63.59 73 56.56 96.72 98 75.93 129.84
24 18.60 31.80 49 37.97 64.92 74 57.34 98.04 99 76.71 131.17
25 19.37 33.12 50 38.74 66.24 75 58.11 99.37 100 77.48 132.49
45
C H A P T E R 7
Technical Data
Alkali Conversion Tables
Equivalence of Sodium Oxide ( Na2O), Caustic Soda (NaOH) and Soda Ash ( Na2CO3)
Na2CO3 Na2O NaOH Na2CO3 Na2O NaOH Na2CO3 Na2O NaOH Na2CO3 Na2O NaOH
1 .5848 .7548 26 15.20 19.62 51 29.82 38.49 76 44.44 57.36
2 1.17 1.51 27 15.79 20.38 52 30.41 39.25 77 45.03 58.12
3 1.75 2.26 28 16.37 21.13 53 30.99 40.00 78 45.61 58.87
4 2.34 3.02 29 16.96 21.89 54 31.58 40.76 79 46.20 59.63
5 2.92 3.77 30 17.54 22.64 55 32.16 41.51 80 46.78 60.38
6 3.51 4.53 31 18.13 23.40 56 32.75 42.27 81 47.37 61.14
7 4.09 5.28 32 18.71 24.15 57 33.33 43.02 82 47.95 61.89
8 4.68 6.04 33 19.30 24.91 58 33.91 43.78 83 48.54 62.65
9 5.26 6.79 34 19.88 25.66 59 34.50 44.53 84 49.12 63.40
10 5.85 7.55 35 20.47 26.42 60 35.09 45.29 85 49.71 64.16
11 6.43 8.30 36 21.05 27.17 61 35.67 46.04 86 50.29 64.91
12 7.02 9.06 37 21.64 27.93 62 36.26 46.80 87 50.88 65.67
13 7.60 9.81 38 22.22 28.68 63 36.84 47.55 88 51.46 66.42
14 8.19 10.57 39 22.81 29.44 64 37.43 48.31 89 52.05 67.18
15 8.77 11.32 40 23.39 30.19 64 38.01 49.06 90 52.63 67.93
16 9.36 12.08 41 23.98 30.95 66 38.60 49.82 91 53.22 68.69
17 9.94 12.83 42 24.56 31.70 67 39.18 50.57 92 53.80 69.44
18 10.53 13.59 43 25.15 32.56 68 39.77 51.33 93 54.39 70.20
19 11.11 14.34 44 25.73 33.21 69 40.35 52.08 94 54.97 70.95
20 11.70 15.10 45 26.32 33.97 70 40.94 52.84 95 55.56 71.71
21 12.28 15.85 46 26.90 34.72 71 41.52 53.59 96 56.14 72.46
22 12.87 16.60 47 27.49 35.48 72 42.11 54.35 97 56.73 73.22
23 13.45 17.36 48 28.07 36.23 73 42.69 55.10 98 57.31 73.97
24 14.04 18.12 49 28.66 36.99 74 43.28 55.86 99 57.90 74.73
25 14.62 18.87 50 29.24 37.74 75 43.86 56.61 100 58.48 75.48
46
C H A P T E R 7
Technical Data
Equations for Converting Hydrometer Readings

Of Liquids Heavier Than Water
AMERICAN STANDARD BAUMÉ: TWADDELL:
145 (0.5 x °Tw)+100
Specific Gravity = Specific Gravity =
145 - °Bé 100
°Tw = (sp gr - 1)200
145(sp gr - 1)
°Bé = sp gr
47
C H A P T E R 8
Methods of Analysis
austic soda is a hazardous, PPG practice is to report % NaOH and Reagents

% Na2O on an “as is” basis, but all
other compounds and metals on an
“A.B.” or anhydrous caustic soda
Standard 1.0N hydrochloric acid
solution
safe handling practices and first aid, basis so that a ready comparison can Phenolphthalein indicator solution
and should wear the recommended be made between 50 percent and 73
protective clothing and equipment percent solutions. Methyl orange-xylene cyanole indica-
(see chapter 3). tor solution
The analytical methods presented here DETERMINATION OF Procedure

were selected on the basis of their SODIUM HYDROXIDE
(NaOH), SODIUM Weigh a sample equivalent to approxi-
ability to provide the most accurate
CARBONATE (Na2CO3) mately 2.0 g of anhydrous sodium
results consistent with simplicity of
AND SODIUM OXIDE hydroxide to 0.1 mg into a tared 10 ml
equipment and acceptable analytical
(Na2O)—TOTAL Teflon or glass weighing bottle and
practices. Many of the techniques
ALKALINITY stopper.
were developed in PPG Industries’ lab-
oratories as improvements on Double End Point Titration
classical methods. The procedures Method
apply to both solution and anhydrous
forms of caustic soda. The applicabili- Abstract
ty to various PPG grades is listed
This method involves titration of the
under each method.
caustic soda sample by a dual end
The laboratories of PPG Industries cus- point titration technique, first to the
tomarily determine trace elements in phenolphthalein end point and then to
caustic soda by spectrometric proce- the methyl orange-xylene cyanole end
dures. On request, PPG personnel will point. The alkali components are cal-
share information on analytical proce- culated from the titration data.
dures and techniques for determining
Application
certain trace substances not listed
here. NaOH, Na2CO3 and Na2O in standard,
Analytical determinations for the following low-iron and rayon grade caustic soda.
substances appear in this chapter:
Na2O grade. Na2CO3 in mercury cell
Page
grade is determined separately by the
Sodium hydroxid total alkalinity . . . . . . 54
Sodium carbonate (low concentrations). . 56
CO2 evolution-conductometric method
Sodium chloride . . . . . . . . . . . . . . . . . . 58 on page 56.
Sodium chloride (low concentrations). . 59 Precision
Sodium sulfate . . . . . . . . . . . . . . . . . . . 60
Sodium sulfate (low concentrations) . . 60 The precision of the method is
Sodium chlorate . . . . . . . . . . . . . . . . . . 61 ±0.10% NaOH, Na2CO3 and Na2O
Sodium chlorate(low concentrations). . 62 by weight.
Iron . . . . . . . . . . . . . . . . . . . . . . . . . . . . 64
48
C H A P T E R 8
Methods of Analysis
Measure approximately 40 ml of 1.0N Calculation cyanole indicator solution. Titrate with
hydrochloric acid solution (slightly less approximately 1.0N hydrochloric acid
than the neutralization requirement % NaOH by weight to the end point.
[A - (B-A)] x N x 0.040 x 100
of the sample) with a burette into a = Weight of Sample (as received)
250 ml beaker. Carefully remove the Normality (N) of the HCl
stopper from the weighing bottle g Na2CO3 x 1000
=
and cautiously submerge both the 53.00 x ml HC1 used
% Na2O by weight
stopper and weighing bottle in the
acid solution. With the aid of a stirring B x N x 0.031 x 100
= 2. METHYL ORANGE-
rod, carefully manipulate the weighing Weight of Sample (as received)
XYLENE CYANOLE
bottle in such a manner that it is
INDICATOR SOLUTION
inverted with no air bubbles existing % Na2CO3 by weight
in the bottle until all the caustic is Dissolve 1.33 g of methyl orange and
2(B-A) x N x 0.053 x 100
dissolved. Permit the bottle and = 3.00 g of xylene cyanole separately in
stopper to remain in the beaker Weight of Sample (as received)
distilled water. Mix them together
during the titration. when they are dissolved and dilute to
% Na2CO3, A.B.* 1 liter with distilled water.
Add 2 drops of phenolphthalein indica-
tor solution and continue titration with % Na2CO3 by weight x 100 Note: With this mixed indicator, alka-
=
standard 1.0N hydrochloric acid solu- % NaOH line solutions are green, acid solutions
tion from the burette until the pink *Anhydrous NaOH basis. are purple-red, and neutral solutions
color begins to fade. are steel-gray.
An alternate procedure for the NaOH
Swirl the weighing bottle in the solu- and Na2CO3 analyses is available Special Equipment
tion and carefully continue the titration which utilizes an automated titrator.
to a colorless end point. Record the A drawing of the 55 ml burette is
Preparation of Reagents and shown on the previous page. The
total volume of acid used in this titra-
Solutions burette contains a 40 ml bulb. Each ml
tion (phenolphthalein end point) to the
nearest 0.01 ml as value “A.” 1. HYDROCHLORIC ACID 1.0N: graduation between 40-55 ml is subdi-
vided into 0.1 ml; 1 ml = 1 inch, NBS
Add 2 drops of methyl orange-xylene Dilute 83 ml of reagent grade concen- accuracy. Graduations are blue stripes
cyanole indicator solution and contin- trated hydrochloric acid, specific on white background. The rate of drain
ue titration to the steel-gray end point. gravity 1.19, with distilled water to is 55 ml per 160-180 seconds.
Record the volume of acid used in the 1 liter in a volumetric flask and mix
total titration to the nearest 0.01 ml as thoroughly. This burette is made under Sketch No.
value “B.” PPG 40476-G by SGA Scientific, Inc.,
Standardization: Weigh 2 ± 0.1 g of 735 Broad Street, Bloomfield, NJ
Record the temperature of the acid anhydrous sodium carbonate (primary 07003, (201) 748-6600.
used for titration and correct the vol- standard) to 0.1 mg into a 250 ml
umes (values “A” and “B”) to 20°C wide mouth Erlenmeyer flask, dissolve
NaOH
(see Temperature Correction Table, in 15 to 20 ml of distilled water, and
page 65). add 2 drops of methyl orange-xylene
49
C H A P T E R 8
Methods of Analysis
DETERMINATION OF of the conductivity cell (24) and bari- urements, check the temperature of
SODIUM CARBONATE um hydroxide reservoir (30) should be the water bath and adjust it to 33°C.
(NA2CO3) of sufficient size and have sufficient Clean the conductivity cell (24) with
capacity to function as a thermal regu- approximately 0.1N hydrochloric acid
CO2 Evolution - lator for these two items of apparatus. and rinse thoroughly with distilled
Conductometric Method The temperature of this environment water. Position the empty cell
must be controlled closely. Operation equipped with the electrodes and inlet
Abstract at 33 ± 0.2°C is recommended in and outlet tubes in the water bath and
order that precise and accurate results make the connections shown in the
The method involves the determination
may be obtained by the procedure. diagram. Purge the system for 15 min-
of sodium carbonate in caustic soda
utes with a slow stream of nitrogen or
by conductometric measurement. The The general procedure first involves air freed of carbon dioxide. Purge gas
method entails the evolution of carbon purging the system with nitrogen or enters at (1) and leaves at (18).
dioxide from the sample by an acidifi- air (free of carbon dioxide) for about
cation and purging process. The 15 minutes prior to introducing a fresh Rinse the conductivity cell with the
liberated carbon dioxide is absorbed in barium hydroxide sample into the con- barium hydroxide solution by manipu-
an excess of barium hydroxide solu- ductivity cell. The proper size sample lation of the stopcocks and application
tion. The change in electrical of caustic soda is then pipetted into of suction through tube (19).
conductivity caused by the absorption the dropping funnel (7) located above
of carbon dioxide to form barium car- the reaction flask (10). The purge Fill the conductivity cell with 0.014N
bonate is the means by which sodium stream is attached to the dropping barium hydroxide solution to some
carbonate is measured. funnel and the sample forced into the predetermined mark on the cell. This
reaction flask to provide minimum mark should be inscribed on the cell
Application body so that fillings of the cell can be
contamination due to carbon dioxide in
the air during the transfer of the sam- duplicated. The mark should be locat-
Mercury cell grade caustic soda.
ple. The dropping funnel is washed ed so that the solution fills the cell a
Precision well with distilled water with the aid little more than halfway.
The precision of the method is of the purge stream, and the system is Add the solution of the weighed sam-
± 0.003% NA2CO3 by weight. purged until a constant ohm reading is ple (equivalent to 6.0 g of anhydrous
obtained from the conductivity cell. caustic soda) to the reservoir (7) and
Special Apparatus and Operation The acid is then introduced into the force it into the sample flask (10) by
reaction flask in a similar manner as connecting the purge stream to the
A conductance bridge is the principle
the sample, and the system is purged top of funnel (7) and opening stopcock
item of special apparatus required for
continuously for 15 minutes. The reac- (8). Wash the reservoir with three 15
the method. The bridge should be
tion flask is heated to 60°C during this ml portions of distilled water using the
capable of measuring differential
period to aid in reducing the solubility purge for forcing the washings into the
resistances of 1 ohm in the desired
of carbon dioxide I the acidified sample. reaction chamber. After the last wash-
concentration range.
Analytical Procedure ing, continue to purge the system at a
NaOH
Other items of apparatus required are rate of 0.1 standard liters per minute
common in most laboratories. The In this procedure actual conductance for 3 minutes and record initial ohm
thermostated water bath (33) for regu- or actual resistance of the solutions is reading. Finally introduce 10 ml of
lating and controlling the temperature measured. Before making any meas- dilute (1:1) sulfuric acid into the sam-
50
C H A P T E R 8
Methods of Analysis
ple flask by way of the reservoir and Calculation 2. STANDARD BARIUM HYDROXIDE
purge stream. The sample must be ABSORBER SOLUTION:
acidified to a pH <3.0 A 6.0-g sample % Na2CO3 by weight
of caustic soda containing 0.05% sodi- grams Na2CO3 from chart x 100 Dissolve 18.7 g of reagent grade bari-
= um hydroxide in 700 ml of boiling
um carbonate (A.B.*) should provide a Weight of Sample (as received)
differential resistance span of approxi- distilled water. After saturation,
mately 21 ohms in a conductivity cell remove any undissolved solids by fil-
% Na2CO3, A.B.* tration and catch the filtrate in a
with a 0.12 cell constant.
Weight % of Na2CO3 x 100 suitably sized reagent bottle contain-
=
Adjust the purge gas flow to 0.1 stan- Weight % NaOH in Sample Tested ing 6.9 l of distilled water which has
dard liters per minute. This operation previously been purged with a slow
facilitates the transfer of any liberated stream of nitrogen to expel carbon
carbon dioxide from the sample into Calibration of Conductivity dioxide. Add a pinch of gelatin, stop-
the absorber solution through the frit- Apparatus per the reagent bottle and mix the
ted glass dispersion tube (17). Measure suitable increments ranging solution thoroughly. The concentration
Continue this sweeping operation for from 1 ml to 10 ml of the standard of this solution should be about
15 minutes. Then check the rate and solution of sodium carbonate (see 0.014N and should be checked by
measure the resistance of the below) into the sample flask (10) and titrating an aliquot of it with standard-
absorber solution with the conductivi- evolve the carbon dioxide into the ized 0.03N hydrochloric acid.
ty bridge. absorber solution as described in the
Record the value and compute the procedure above. The same purge rate DETERMINATION OF
change in resistance of this solution (0.1 standard liters per minute) should SODIUM CHLORIDE (NaCl)
resulting from the formation of barium be used in the calibration and in the
Volhard Method
carbonate. sample procedure. Prepare a calibra-
tion chart for the apparatus from these Abstract
For results of greatest accuracy it is data, relating the number of grams of
desirable to run a blank test with dis- sodium carbonate and the resistance The chloride in caustic soda is deter-
tilled water in place of the sample and span of the absorber solution. mined according to the Volhard
make an appropriate blank correction. titration method. The method entails
Special Reagents and Solutions the acidification of the sample with
When the determination is completed, nitric acid and the subsequent titration
remove the acidified sample solution 1. STANDARD SOLUTION
of the chloride with standard silver
by draining through stopcock (12) at OF SODIUM CARBONATE:
nitrate and standard potassium thio-
the bottom of the flask. Rinse the flask Dissolve 0.1000 g of reagent grade, cyanate solutions.
thoroughly with distilled water in anhydrous sodium carbonate in freshly
preparation for future tests. Remove Application
boiled and cooled distilled water and
“spent” barium hydroxide solution dilute to 100 ml in a volumetric flask. Standard, low-iron and rayon grade
from the conductivity cell by suction One ml of this solution contains caustic soda (not applicable to
through connection (19).
NaOH
0.001 g of sodium carbonate. mercury cell grade caustic soda).
Consult the calibration chart (see
below) to obtain the number of grams
of sodium carbonate in the sample.
51 *Anhydrous NaOH basis.
C H A P T E R 8
Methods of Analysis
Precision color persists. Compute the net vol- To dilute a solution with water:
ume in ml of standard silver nitrate A-D
The precision of the method is ± solution consumed. xX=Y
0.10% NaCl by weight. D
Calculation To strengthen a weak solution with a
Reagents stronger solution:
% NaCl by weight D-A
Standard 0.1N silver nitrate solution xY=X
(corrected to 20°C) = (ml AgNO3 x N) - (ml KCNS x N) C-D
x 0.0585 x 100 where A = Actual concentration
Standard 0.1N potassium thiocyanate Weight of Sample (as received) of the solution that is
solution (corrected to 20°C) to be corrected
% NaCl, A.B.*
Concentrated nitric acid (C.P.), sp gr % NaCl by Weight x 100 D = desired concentration
= C = concentration of
1.42 % NaOH•by Weight
strengthening solution
Ferric nitrate indicator solution
Preparation of Special Reagents X = amount of stronger
Procedure solution to be added,
and Solutions
Weigh a sample equivalent to approxi- taken, or prepared
1. PREPARATION AND STANDARDI-
mately 10 g of anhydrous sodium Y = amount of weaker
ZATION OF SILVER NITRATE AND
hydroxide to 0.1 g into a 250 ml solution or water
POTASSIUM THIOCYANATE:
beaker, and add 35 ml of distilled to be added or taken
water. Add 2 ml of ferric nitrate indica- Preparation of 0.1N Silver Nitrate:
tor solution and neutralize with Standardization: Dry a small quantity
concentrated nitric acid till iron precip- Dissolve 17 g ± 0.1 g of silver nitrate of potassium chloride (A.R.) in the
itate dissolves. Then add 1 to 2 ml in distilled water. Add 5.5 ml of con- drying oven for 2 hours. Weigh 0.07
excess. centrated nitric acid and dilute to 1 grams ± 0.1 mg of dry, cool potassi-
liter. um chloride into a weighing bottle.
Add 0.2 ml of standard 0.1N potassi- Dissolve the potassium chloride in
um thiocyanate from a burette and Preparation of 0.1N Potassium
water and wash it into a 250 ml
titrate slowly with standard 0.1N silver Thiocyanate: Dissolve 9.78 g ± 0.1 g
beaker. Titrate according to the
nitrate solution until the red color dis- potassium thiocyanate (A.R.) in dis-
general procedure.
appears. Then add an excess of at tilled water and dilute to one liter.
least 2 ml. Stir vigorously until the sil- AgNO3 Normality
If it is desirable to adjust the silver
ver chloride coagulates. Quantitatively nitrate and potassium thiocyanate to Grams KC1
filter the sample through a medium- =
exactly the same normality, titrate a 0.07456 [ml AgNO3 - (ml KCNS) x C
porosity sintered-glass filter to remove quantity of the potassium thiocyanate
the silver chloride precipitate. Wash with silver nitrate according to the KCNS Normality = AgNO3 Normality x C
the precipitate with 5% nitric acid until procedure and determine the ratio of
NaOH
it is free of silver nitrate. Back-titrate standard solution.
the excess silver nitrate in the filtrate
ml AgNO3
with standard 0.1N potassium thio- C=
cyanate solution until a faint rust-red ml KCNS
*Anhydrous NaOH basis.

52
C H A P T E R 8
Methods of Analysis
2. FERRIC NITRATE INDICATOR Reagents At the end of the digestion period
SOLUTION transfer a sufficient amount of the
Phenolphthalein indicator solution blank solution to the 5 cm comparison
Dissolve 100 g of ferric nitrate (A.R) in cell of the spectrophotometer and
distilled water and add 100 ml nitric Dilute nitric acid (1:1)
measure the light transmittance of the
acid (C.P.) sp gr 1.42. Dilute to one Standard silver nitrate solution (0.1N) blank at 425 ml. Record the transmit-
liter. tance value.
Procedure
Note: For assay work the solutions Repeat this measurement with the
should be standardized on the day Weigh a sample equivalent to approxi-
prepared sample solution, and record
used and titrant volumes corrected to mately 5 g of anhydrous sodium
the transmittance value. Compute the
20°C per table on page 65. An alter- hydroxide to 0.1 g into a 250 ml
grams of chloride in the sample (blank-
nate procedure for the Vilhard salt beaker. Dilute the sample with 20 ml
corrected) from a previously prepared
method is available which utilizes an of distilled water, chloride-free. Add 1
calibration for the spectrophotometer
automated titrator. drop of phenolphthalein indicator solu-
(see below).
tion and neutralize the sample solution
DETERMINATION OF LOW cautiously by the addition of dilute Calculation
CONCENTRATIONS OF (1:1) nitric acid. Render the solution
slightly acidic by adding 1 drop of acid % NaCl by weight
SODIUM CHLORIDE (NaCl)
in excess. = Grams of Cl¯ from Chart
Turbidimetric Method x 1.6483 x 100
Transfer the solution to a 100 ml volu-
Weight of Sample (as received)
Abstract metric flask, cool to room
temperature, and dilute to the mark % NaCl, A.B.*
The method involves the measurement
with distilled water. Prepare another
of low concentrations of sodium chlo- = % NaCl by wieght x 100
100 ml volumetric flask filled to the % NaOH by weight
ride by a turbidimetric procedure. The
mark with distilled water containing
method entails reaction of the acidified
the same amount of phenolphthalein
sample with an excess of silver Calibration of Spectrophotometer
indicator and excess acid as used in
nitrate. The resulting turbidity due to
the sample above. This solution serves Standard Chloride Solution:
silver chloride is determined spec-
as a blank.
trophotometrically.
Weigh 2.1143 grams of oven-dried,
Add 1 ml of diluted (1:1) nitric acid reagent-grade potassium chloride and
Application solution to both the sample and blank transfer to a 1000 ml volumetric flask.
Mercury cell grade caustic soda. solutions in the flasks. Mix thoroughly. Dissolve the salt in distilled water and
Add 1 ml of 0.1N silver nitrate solution dilute to the mark. Mix thoroughly.
Precision to each flask and mix by inverting
The precision of the method is once only, then set aside in the dark Measure a 10 ml aliquot portion of this
±0.002% NaCl by weight. for 15 minutes. The total volume of the solution into another 1000 ml volumet-
sample and standard solutions in the ric flask and dilute to the mark with
NaOH
100 ml flasks is 102.0 ml. It is not distilled water. Mix thoroughly. One ml
necessary to standardize the silver of the resulting solution contains
nitrate solution volumetrically for 0.00001 g of chloride.
this test.
53
C H A P T E R 8
Methods of Analysis
Standardization Procedure Application Since the spectrophotometric meas-
urements are made against a reagent
Prepare a series of standards by All grades of caustic soda. blank containing 7.3 g of sodium chlo-
measuring 1.0, 3.0, 5.0 and 10.0 ml of ride, its preparation should be initiated
the standard chloride solution respec- Precision
at this point in the analysis.
tively into a series of 100 ml The precision of the method is
volumetric flasks. Dilute each standard ± 0.00005% Fe by weight. Weigh 7.3 g of purified sodium chlo-
to 100 ml with distilled water and mix ride (iron-free) into a 100 ml
thoroughly. Proceed with the turbidity Reagents volumetric flask and dissolve in
development and measurement approximately 50 ml of distilled water.
Concentrated hydrochloric acid (C.P.),
according to the directions given Add 0.5 ml of dinitrophenol indicator
sp gr 1.19
above for the samples. Conduct the solution and neutralize by dropwise
turbidimetric measurements versus Hydroxylamine hydrochloride solution, additions of concentrated hydrochloric
distilled water in the reference cells. 10% W/V acid or ammonium hydroxide, then
From these data prepare a calibration render the solution slightly acidic by
curve. Acetate buffer solution adding two drops of concentrated
o-Phenanthroline solution, 1% W/V hydrochloric acid.
DETERMINATION OF IRON To both the sample and blank, add 1
(Fe) 2,4-Dinitrophenol indicator solution,
0.1% W/V ml of 10 percent hydroxylamine
o-Phenanthroline Colorimetric hydrochloride solution and mix thor-
Method Sodium chloride crystals (purified oughly. Allow the solutions to digest
grade) 10 minutes to effect reduction of the
Abstract iron to the ferrous state. After reaction
Procedure add 10 ml of the acetate buffer solu-
The method involves the determination
Weigh a sample equivalent to 5.0 g of tion and mix thoroughly. The pH of this
of iron in caustic soda by the spec-
anhydrous sodium hydroxide to 0.1 g solution should be between 4 and 5.
trophotometric measurement of the
into a 125 ml beaker and dilute to 50 Add 5 ml of ortho-phenanthroline solu-
iron ortho-phenanthroline complex.
ml with distilled water. Add 0.5 ml of tion, dilute to 100 ml with distilled
The method entails acidification of the
dinitrophenol indicator solution and water and mix the solutions thoroughly.
sample with hydrochloric acid, treat-
ment with a solution of hydroxylamine neutralize the sample with concentrat- Allow the solutions to stand for 15
hydrochloride to reduce the iron to ed hydrochloric acid. Cool the solution minutes, then transfer an appropriate
Fe(II), adjustment of the pH value of to room temperature and then render volume of the prepared solutions
the solution, and the addition of the slightly acidic by the addition of two to a 5 cm comparison cell of the
complexing agent orthophenanthroline drops of concentrated hydrochloric spectrophotometer. Measure the
solution. The color of the solution is acid. Transfer the slightly acidic solu- transmittance of the sample at
measured spectrophotometrically at a tion to a 100 ml volumetric flask and 510 mµ as compared with the blank.
wavelength of 510 mµ. The procedure reserve.
Consult the calibration curve for the
NaOH
is standardized and performed in a
sodium chloride matrix. spectrophotometer to obtain the num-
ber of grams of iron in the sample.

54
C H A P T E R 8
Methods of Analysis
Calculation aliquot of this solution to 1000 ml and Volumetric Temperature
mix. One ml of the resulting solution Correction Table
% Fe by weight contains 0.00001 g of iron.
g Fe from Calibration Curve x 100 Water and 0.1N
= 2. ACETATE BUFFER SOLUTION: Temperature, Solutions, 1N
Weight of Sample (as received)
°C ml/l1 HCl2
Dissolve 272 grams of sodium acetate 15 +0.77 +0.97
Fe, A.B.* trihydrate in 500 ml of distilled water. 16 +0.64 +0.79
% Fe by weight x 100 Add 250 ml of glacial acetic acid, cool 17 +0.50 +0.61
= and dilute to one liter with distilled 18 +0.34 +0.41
% NaOH by weight
water. 19 +0.18 +0.21
20 0 0
3. o-PHENANTHROLINE SOLUTION, 21 -0.18 -0.22
Calibration of Spectrophotometer
1% (W/V): 22 -0.38 -0.44
Place 7.3 g of pure sodium chloride 23 -0.59 -0.67
Dissolve 5.0 g of 1,10-ortho-phenan-
(iron-free) into a series of 100 ml volu- 24 -0.81 -0.91
throline in methyl alcohol and dilute to
metric flasks and dissolve the salt in 25 -1.03 -1.17
500 ml with alcohol. Store this solu-
approximately 30 ml of distilled water. 26 -1.27 -1.43
tion in a glass-stoppered amber bottle.
Measure 0.0, 0.5, 1.0, 2.0, 4.0, 7.0, 27 -1.52 -1.70
Prepare fresh solution each 3 to 4 28 -1.77 -1.98
and 10.0 ml respectively of the stan-
weeks. 29 -2.04 -2.26
dard iron solution into the flasks.
4. 2,4-DINITROPHENOL INDICATOR 30 -2.31 -2.55
Add 0.5 ml of dinitrophenol indicator
SOLUTION 0.1% (W/V):
solution and neutralize by the drop- 1
“Handbook of Chemistry and Physics,” 48th
wise addition of ammonium hydroxide, Dissolve 0.1 g of 2,4-dinitrophenol in ed, The Chemical Rubber company,
then render the solution slightly acidic distilled water and dilute to 100 ml. Cleveland, Ohio, 1967-1968, p F2.
by the addition of 2 drops of concen- 2
“Chemical Annual,” 7th ed, D.Van Nostrand
trated hydrochloric acid. Proceed with 5. HYDROXYLAMINE HYDRO-
Company, Inc., Princeton, New Jersey,
the preparation of the standards as CHLORIDE SOLUTION, 10% (W/V): 1934, p 71.This table gives the correction to
described in the procedure above. Dissolve 50 g of hydroxylamine be added per liter to the observed volume of
Construct a calibration curve from the water, or standard 0.1N solution, to give the
hydrochloride in distilled water and volume at the standard temperature 20°C.
calibration data. dilute to 500 ml. An alternative Conversely, by applying the corrections to
Special Reagents and Solutions method is available utilizing optical the volume desired at 20°C, the volume that
emission spectrography. must be measured out at the designated
1. STANDARD IRON SOLUTION: temperature in order to give the desired vol-
ume at 20°C will be obtained. The volumes
Dissolve 0.1000 g of iron (A.R.) in a are measured in glass apparatus having a
mixture of 20 ml of hydrochloric acid coefficient of cubical expansion of 0.000025
per degree C.
and 50 ml of distilled water. Heat the
mixture gently to expedite solution of
NaOH
A formula for calculating volumetric
the iron metal. When the solution is temperature corrections appears
dissolved, dilute it to 1 liter with dis- in “ASTM Standards,” Part 22, 1968,
tilled water and mix. Dilute a 100-ml Designation E-200-67, page 457.

55
C H A P T E R 9
Uses of Caustic Soda

austic soda is a hazardous,

and should wear the recommended
(see chapter 3).
Caustic soda has a host of different
uses. Its major markets are the chemi-
cal and pulp and paper industries, but
considerable quantities of caustic soda
are used to produce rayon, aluminum,
soap, textiles and petroleum. Other
high-volume uses include detergents
and cleaners, boiler compounds,
paint-and varnish-removers, water
treatment, food processing and leather Caustic soda is important in the
manufacturing. manufacture of aluminum.
Because of inherent processing advan-

tages, caustic soda is replacing soda
ash (sodium carbonate) as a source of Chemical processing is the major user
sodium oxide in several uses. These of caustic soda.
include the manufacture of glass,
paper pulp, phosphates and silicates,
and water-treatment.
Caustic soda is a major processing chemical

for pulp and paper.
56 NaOH
C H A P T E R 10
Methods of Manufacture
austic soda is a hazardous, The diaphragm cell method is a one-

step process. The over-all reaction is:
Sodium
Chloride + Water → Chlorine + Hydrogen +
Sodium
Hydroxide
Direct
and should wear the recommended 2NaC1 + 2H20 → C12 + H2 + 2NaOH
Current
(see chapter 3).
The earlier diaphragm cells consisted formation of caustic and chlorine can
of a shell having a concrete bottom, a be maintained.
LIME-SODA PROCESS steel mid-section, and a concrete top.
The electrodes consisted of a graphite The electrolyte in the cell is a colution
The lime-soda process was the only of sodium chloride. Natural salt, how-
commercial method of manufacturing anode and a steel wire mesh cathode.
With the conversion to the dimension- ever, contains varying quantities of
caustic soda until 1890, when calcium, magnesium and other impuri-
processes for simultaneous production ally stable anodes (DSA) in the early
1970s and improved materials of con- ties. The brine is treated to remove
of caustic soda and chlorine by the these contaminants by precipitation.
electrolysis of brine were introduced. struction, several changes in
diaphragm cell design occurred. The brine is then filtered to remove the
Lime-soda process techniques precipitates and any other undissolved
improved over the centuries from the Instead of using concrete tops and
bottoms, the modern diaphragm cells solids that may be present. At this
time soap was made in ancient days, stage the brine has too low a concen-
but every process still depended on are constructed with steel bottoms
and plastic tops. The DSA anodes are tration of sodium chloride for efficient
the reaction of slaked lime (calcium cell operation. It is brought to the
hydroxide) with soda ash (sodium titanium with an electrolytic coating.
The cathode is still steel but in select- desired strength either by addition of
carbonate) to produce caustic soda purified salt or by evaporation of some
(sodium hydroxide) and calcium ed cases an electrolytic coating is
used. The conversion to DSA anodes of the water.
carbonate.
provided a significant reduction in the For convenience, cells are arranged in
In chemical notation: cell power consumption. The diagram series electrically, each circuit consist-
on the facing page shows a ing of several rows of cells. Two rows
Calcium Sodium Sodium Calcium
design of a modern monopo- share a brine distribution line and col-
Hydroxide Carbonate Hydroxide Carbonate
lar diaphragm cell. lecting systems for chlorine and
Ca(OH)2 + Na2CO3 → 2NaOH + CaCO3
The anode and cathode are hydrogen. On the aisle side of each
separated by a “diaphragm” made row is a pipe line for collecting caus-
DIAPHRAGM CELL tic. Brine flow to each cell is
from a deposited layer of asbestos
PROCESS individually controlled.
fiber that coats each cathode. The
After 1890, the number of electrolytic diaphragm serves to keep the caustic When direct current electricity flows
chlor-alkali plants increased until, by soda and hydrogen separated from the between anodes and cathodes and
1940, most caustic soda was pro- anolyte, but it also has an additional through the brine, chlorine collects at
NaOH
duced by the electrolysis of brine. function by controlling the flow of the anode plates and hydrogen col-
electrolyte to the cathode. In this man- lects inside the cathode screen.
ner, the optimum efficiency in Sodium combines with the hydroxyl
57
C H A P T E R 10
ion of water to form caustic soda
(sodium hydroxide) at the cathodes.
The chlorine bubbles up through the
brine and is carried away by the chlo-
rine-collecting system. Similarly,
hydrogen is collected from the cath-
ode section. The caustic solution is
drawn off from the cell’s lower side.
The caustic solution as it comes from
the cell is approximately 12 percent
sodium hydroxide. The solution is
evaporated to 50 percent or 73 per-
cent sodium hydroxide. The latter can
be further concentrated to the anhy-
drous state and sold in the form of
PELS caustic soda beads.
Above, circuit of diaphragm cells with dimensionally stable anodes. Below, Diaphram Cell.
58 NaOH
C H A P T E R 10
BIPOLAR DIAPHRAGM bipolar cell design. These bipolar electrolyzers is substantially less than that
ELECTROLYZERS trolyzers were commercialized in 1973. of monopolar diaphragm cells.
The diaphragm cells just described are The bipolar electrolyzers have dimen- Each cell of a bipolar electrolyzer has
classed as monopolar; each cell in a sionally stable metal anodes made of its own brine reservoir made of fiber-
series circuit is connected by bus titanium coated with mixed metal glass-reinforced polyester. The reservoir
bars. Bipolar electrolyzers consist of a oxides. A constant small gap is main- provides an emergency stand-by supply
number of bipolar diaphragm cells, tained between anode and cathode, of brine in case brine flow to the cell
usually eleven, in a series circuit of up minimizing resistance loss through the should be temporarily stopped.
to 20 electrolyzers. The bipolar design electrode. Because the open design of
permits current to flow internally with- the dimensionally stable anodes lets Bipolar electrolyzer cell rooms have
in an electrolyzer from one cell to the chlorine escape from behind, the portable cutout switches which permit
another, instead of through external resistive path in front of the anodes is single electrolyzers to be taken out of
bus bars, which are needed only also reduced. service without interrupting the opera-
between electrolyzers. tion of an entire circuit. The
The bipolar design also lowers the electrolyzer can be removed from the
The bipolar electrolyzer design is the resistance through the electrolyte and cell room to a cell renewal facility by a
result of a joint development effort in the fastenings and connections transporter system.
begun by PPG and de Nora in 1969 after between cells of an electrolyzer. As a
many years of working separately on result, the cell voltage of bipolar elec- Major benefits of the bipolar elec-
trolyzer include lower power
consumption, high current efficiency,
and reduced floor space requirement.
59 NaOH
Bipolar Diaphragm Electrolyzer.
C H A P T E R 10
MERCURY CELL PROCESS
The mercury cell is really two cells. In
the primary unit, chlorine and sodium
are released by electrolysis of brine;
the chlorine is drawn off, and the sodi-
um dissolves in the mercury cathode,
forming an amalgam. In the secondary
unit, the sodium in this amalgam
reacts with water, forming sodium
hydroxide and releasing hydrogen. The
reaction for this method is shown.
The mercury cell process is in two
steps. The overall reaction in the pri-
mary cell is:
Direct
2NaCl + (Hg)x →
Current
2Na + (Hg)x +
Cl2
The sodium produced at the cathode
dissolves in the mercury to form an
amalgam. The overall reaction in the
secondary cell is:
Direct
2Na(Hg)x + 2H2O →
Current
2NaOH
+ H2 + 2(Hg)x
There are several different types of
mercury cells, some vertical, some
horizontal. PPG Industries Chemicals
Group uses two types of horizontal
cells, the German-designed Uhde cells
and the Italian de Nora cells. The pri-
mary cell is a broad, shallow steel
trough, quite long, although shorter
than an average battery of diaphragm
cells. The top is a tightly fitting flat
steel plate, or rubber cover.
Bipolar element of electrolyzer. The sides of the cell and the underside
NaOH
of the cover, which come into contact
with chlorine, are protected by a rub-
ber lining.
60
C H A P T E R 10
The cathode is a slowly flowing graphite grids form the cathode. MEMBRANE CELL PROCESS
stream of mercury which spreads Anode and cathode are in contact. The
across the floor of the cell. The mercu- cell functions, in effect, like an inter- The membrane cell in many respects
ry inlet end of the cell is slightly higher nally shorted battery. is similar to a diaphragm cell except
than the outlet end, so that the desired that a high strength, high purity
rate of flow is maintained by gravity. Raw brine for the mercury cell process caustic is produced at the cell.
The metal anodes are dimensionally is purified and concentrated in much Both monopolar and bipolar cells are
stable and mounted with the broad the same way as for the diaphragm available. The use of an ion exchange
face parallel to the mercury bed. cell process. The effluent of brine from membrane in lieu of an asbestos
Vertical position of anodes is the mercury cell is depleted by partial diaphragm and nickel instead of
adjustable from outside the cell, per- removal of chlorine and sodium. This steel construction for the cathode
mitting maintenance of optimum brine is recovered, resaturated and compartment constitute the major
space between anodes and cathode recirculated. design differences. A schematic of
(see diagram shown below). a membrane cell is shown on the
The amalgam from the primary cell following page.
The secondary cell, at one side of the flows to the secondary cell. Pure
primary, is of the same length but is water flows over this amalgam; its Brine treatment for the membrane
much smaller in cross-section and is decomposition is aided by the electric cell process is the same as for the
unlined. This cell is operated so that current between the amalgam and the diaphragm cell except that the purified
the mercury becomes the anode; graphite grids; hydrogen is liberated brine is passed through an ion
and caustic soda solution is formed. exchange resin. Also, since the brine
does not pass through the membrane,
the depleted brine from the cell is nor-
mally recirculated in a closed loop
system. This requires dechlorinating
and resaturating the brine. The brine in
selected situations is used on a “once
through basis” by resaturating the
depleted brine and feeding it to a
diaphragm cell circuit.
In the electrolysis of brine, chlorine is
produced at the anode. The sodium
ion that is generated is selectively
allowed to pass through the mem-
brane. In the cathode compartment,
hydrogen is produced at the cathode
with the sodium ion reacting with the
hydroxyl ion to the caustic soda. The
caustic solution is recirculated and
deionized water added to maintain the
sodium hydroxide concentration at
normally between 32 to 35% depend-
ing on the membrane used. For certain
61
C H A P T E R 10
membranes, a lower caustic concen-
tration must be maintained.
Because of the higher caustic
strength, the cathode compartment is
generally constructed with nickel.
Since the nickel cathode is not as
good an electrode material as steel, an
electrolytic cathode coating is general-
ly used to minimize the cell power
consumption.
The caustic solution from the cells can
be used “as is” for most captive
requirements or evaporated to 50 per-
cent employing a relatively simplistic
evaporator system. This high purity
caustic can also be concentrated to 73
percent or to anhydrous caustic soda.
62 NaOH
C H A P T E R 10
PPG INDUSTRIES, Inc. Trademarks used in this issue:

440 College Park Drive not representations or warranties of
PELS is a registered trademark performance, results or comprehen-
Monroeville, PA 15146
of PPG Industries, Inc. siveness of such data, nor do they
(800) 243-6774
imply any recommendations to infringe
Valeron is a registered trademark any patent or an offer of license under
of Illinois Tool Works, Inc. any patent.
Monel and Inconel are trademarks If not properly used, the products men-
of Inco Alloys International, Inc. tioned herein can be hazardous. All
Ampco is a trademark purchasers of these products should
of Ampco Metal, Inc. communicate all the health and safety
information contained herein to their
Ni-Resist is a trademark customers or employees, as the case
of Thomas Foundries, Inc. may be. PPG Industries recommends
that, before anyone uses or handles
Teflon is a registered trademark of
the products mentioned herein, he
DuPont.
should read and understand the pre-
Every effort has been made to cautionary and other information on
acknowledge known trademarks of the product label, as well as in the
other companies. All other trademarks Material Safety Data Sheet and
are properties of their respective owners. Product Bulletin.
The statements and methods present- Although the products mentioned here-
ed about the products mentioned in are intended for industrial and
herein are based upon the best avail- manufacturing uses, they are potential-
able data and practices known to PPG ly hazardous materials and must be
Industries at the present time, but are kept out of the reach of children.
63 NaOH #0100 Rev 0406 pdf

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©2008 PPG Industries, Inc.

Caustic Soda Can Cause Severe Burns to Skin and Eyes

EMERGENCY TELEPHONE NUMBER

C reactive chemical. Before

Tank Cars and Tank Trucks

C reactive chemical. Before

The entire palette load, (foreground) 1 1/2

Drumming PELS caustic soda beads.

verconfidence can be A deceptive aspect of caustic soda is Eyes

O responsible for serious per-

austic soda is a hazardous,

C reactive chemical. Before

problems. For example, a 20% solution

C reactive chemical. Before

out with compressed air to prevent

If the internal valve cannot be opened

METHODS OF UNLOADING 5. Removing plug requires two

Preparing Empty Cars for Return Unloading Tank Trucks

C reactive chemical. Before

CSD (CLOSED SYSTEM Advantages of CSD Rail Car 5. ALL-WEATHER OPERATION:

Automatic loading of piping of pressure

CSD bulk unloading system for rail cars.

opened. Anhydrous caustic soda can investment for a system to receive

C reactive chemical. Before

Note: Table data based on water at 39.2°F (4°C).

Note: Table data based on water at 39.2°F (4°C).

2 1.55 1.023 3.26 4.6 21 1.17 1.28 8.53 63.80

52 40.30 1.49 47.68 98 774 6.46 48.32 12.42 92.93

64 49.60 1.61 54.94 122 1030 8.59 64.27 13.42 100.42

2 1.10 0.90 0.72 0.62 0.52 0.44

Equations for Converting Hydrometer Readings

C reactive chemical. Before

The analytical methods presented here DETERMINATION OF Procedure

*Anhydrous NaOH basis.

*Anhydrous NaOH basis.

*Anhydrous NaOH basis.

Uses of Caustic Soda

C reactive chemical. Before

Because of inherent processing advan-

Caustic soda is a major processing chemical

C reactive chemical. Before

PPG INDUSTRIES, Inc. Trademarks used in this issue:

63 NaOH #0100 Rev 0406 pdf

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