Unit 14 - Gravimetric Analysis-Subjects Autosaved 1 0
Unit 14 - Gravimetric Analysis-Subjects Autosaved 1 0
Unit 14 - Gravimetric Analysis-Subjects Autosaved 1 0
Objectives
Introduction
Gravimetric methods are quantitative methods that are based on measuring the mass of a
pure compound to which the analyte is chemically related. Since weight can be measured
with greater accuracy than almost any other fundamental property, gravimetric analysis is
potentially one of the most accurate classes of analytical methods . However it is lengthy
and tedious as a result, only a very few gravimetric methods are currently used . There are
three fundamental types of gravimetric analysis . In precipitation gravimetry, which is
our subject in this unit , the analyte is separated from a solution of the sample as a
precipitate and is converted to a compound of known composition that can be weighed .
In volatilization gravimetry, the analyte is separated from other constituents of a sample
by conversion to a gas . The weight of this gas then serves as a measure of the analyte
concentration . In electrogravimetry, the analyte is separated by deposition on an
electrode by an electrical current. The mass of this product then provides a measure of the
analyte concentration.
Unit 14
Last update : 1/5/2014 GRAVIMETRIC ANALYSIS Subjects
Subjects
The precipitate often contains ions that where trapped when the precipitate was formed.
This is mostly a problem for crystalline precipitates. If the trapped ions are not volatile,
then their presence will corrupt the weighing step. Concentration of interfering species
may be reduced by digestion. Unfortunately , postprecipitation as we will see later will
increase during digestion .
4-Washing and Filtering
Problems with surface adsorption may be reduced by careful washing of the
precipitate. With some precipitates, peptization occurs during washing. Each particle of
the precipitate has two layers , in primary layer certain ions are adsorbed and in the outer
layer other ions of opposite charge are adsorbed . This situation makes the precipitate
settle down . If the outer layer ions are removed then all the particles will have the same
charge so the particles will be dissonant . This is called peptization .
Unit 14
Last update : 1/5/2014 GRAVIMETRIC ANALYSIS Subjects
Subjects
This results in the loss of part of the precipitate because the colloidal
form may pass through on filtration. , in case of colloidal precipitates we
should not use water as a washing solution since peptization would occur. In
such situations dilute volatile electrolyte such as nitric acid, ammonium
nitrate, or dilute acetic acid may be used.
Usually, it is a good practice to check for the presence of precipitating agent
in the filtrate of the final washing solution. The presence of precipitating
agent means that extra washing is required. Filtration should be done in
appropriate sized Goosh or ignition ashless filter paper. After the solution has
been filtered, it should be tested to make sure that the analyte has been
completely precipitated. This is easily done by adding a few drops of the
precipitating reagent to the filtrate ; if a precipitate is observed, the
precipitation is incomplete.
Unit 14
Last update : 1/5/2014 GRAVIMETRIC ANALYSIS Subjects
Subjects
The common ion effect can be used to reduce the solubility of the precipitate. When Ag+
is precipitated out by addition of Cl-
Ag+ + Cl- → AgCl (s)
The (low) solubility of AgCl is reduced still further by the excess of Ag+ which is added,
pushing the equilibrium to the right . It important to know that the excess of the
precipitating agent should not exceed 50% of its equivalent amount , otherwise the
precipitating agent may form a soluble complex with the precipitate :
AgCl + Cl- → AgCl2- ( soluble complex )
The following graph shows that most precipitates follow this pattern, but there are some
anomalies such as Hg2I and BaSO4 .
Unit 14
Last update : 1/5/2014 GRAVIMETRIC ANALYSIS Subjects
Subjects
5- Drying and Ignition: The purpose of drying (heating at about 120-150 oC in an oven) is to
remove the remaining moisture while the purpose of ignition in a muffle furnace at
temperatures ranging from 600-1200 oC is to get a material with exactly known chemical
structure so that the amount of analyte can be accurately determined . The precipitate is
converted to a more chemically stable form. For instance, calcium ion might be precipitated
using oxalate ion, to produce calcium oxalate (CaC2O4) which is hydrophil , therefore it is
better to be heated to convert it into CaCO3 or CaO . The CaCO3 formula is preferred to
reduce weighing errors as mentioned in previous lectures .
Unit 14
Last update : 1/5/2014 GRAVIMETRIC ANALYSIS Subjects
Subjects
The precipitate can be carefully heated in a crucible until the filter paper has burned
away; this leaves only the precipitate. (As the name suggests, "ashless" paper is
used so that the precipitate is not contaminated with ash.) . If you use Goosh
crucible then after the precipitate is allowed to cool (preferably in a desicator to
keep it from absorbing moisture), it is weighed (in the crucible).
Unit 14
Last update : 1/5/2014 GRAVIMETRIC ANALYSIS Subjects
Subjects
VIDEO
http://www.youtube.com/watch?v=4NfLk-2cEic#t=106 You Tube
Unit 14
Last update : 1/5/2014 GRAVIMETRIC ANALYSIS Subjects
Subjects
Impurities in Precipitates
Impurities in Precipitates No discussion of gravimetric analysis would be complete
without some discussion of the impurities which may be present in the precipitates.
There are two typs of impurities :
a. Coprecipitation
This is anything unwanted which precipitates with the analyte during precipitation .
Coprecipitation occurs to some degree in every gravimetric analysis (especially
barium sulfate and those involving hydrous oxides). You cannot avoid it all what you
can do is minimize it by careful precipitation and thorough washing :
1- Surface adsorption
Here unwanted material is adsorbed onto the surface of the precipitate. Digestion of a
precipitate reduces the amount of surface area and hence the area available for surface
adsorption. Washing can also remove surface material.
Unit 14
Last update : 1/5/2014 GRAVIMETRIC ANALYSIS Subjects
Subjects
Impurities in Precipitates
2- Occlusion
This is a type of coprecipitation in which impurities are trapped within the growing crystal.
And can be reduced by digestion and reprecipitation .
b. Postprecipitation
Sometimes a precipitate standing in contact with the mother liquor becomes contaminated
by the precipitation of an impurity on top of the desired precipitate .To reduce
postprecipitation filter as soon as the precipitation is complete and avoid digestion .
Unit 14
Last update : 1/5/2014 GRAVIMETRIC ANALYSIS Subjects
Subjects
Precipitating Agents
Precipitating Agents :
Ideally a gravimetric precipitating agent should react specifically or at least
selectively with the analyte. Specific reagents which are rare, react only with a
single chemical species. Selective reagents which are more common, react with
a limited number of species. In addition to specificity and selectivity, the ideal
precipitating reagent would react with analyte to give a precipitate that has the
preferred requirements which have been previously discussed.
Inorganic precipitating agents :
The inorganic precipitants e.g. S2- , CO32- , PO43- …etc are usually not
selective
compared to the organic precipitants but it give precipitates with well known
formula .
Unit 14
Last update : 1/5/2014 GRAVIMETRIC ANALYSIS Subjects
Page.No
Precipitating Agents
weight of analyte ( g )
% analyte X 100
weight of sample ( g )
Example : A 0.5962 g sample of iron ore is dissolved in perchloric acid (HClO4). All iron
present is oxidized to Fe3+. The solution is filtered to remove solid matrix materials and made
basic with addition of ammonium hydroxide. The iron precipitates as the Fe(OH)3 .xH2O gel.
The precipitate is collected in a cistern crucible and ignited to produce Fe2O3. What is the wt.
% of iron in the sample if the analysis produced 0.3210 g Fe2O3?
Solution : The overall reaction is :
2 Fe3+ + 3 OH- → Fe2O3 + 3/2 H2
From this we derive the gravimetric factor relating weight of final material to the weight of
iron analyte :
Unit 14
Last update : 1/5/2014 GRAVIMETRIC ANALYSIS Subjects
Subjects
VIDEO VIDEO
You Tube My Channel
Unit 14
Last update : 1/5/2014 GRAVIMETRIC ANALYSIS Subjects
Subjects
Example : You have 10 mL of 0.1 M solution of S2- and you want to precipitate S2- as
Ag2S . Calculate the volume of 0.2 M solution of Ag+ which must be added to achieve
complete precipitation ?
Solution :
2 Ag+ + S2- ↔ Ag2S
mmoles S2- = 10 X 0.1 = 1
mmoles Ag+ ( equivalent ) = mmoles S2- X 2/1 =1X 2/1= 2
mmoles Ag+ required for complete precipitation = mmoles Ag+ ( equivalent ) + 50% of 2 mmole
= 2 + 1 = 3
mmoles Ag+ = M X Vol. (mL)
3 = 0.2 X Vol. (mL)
Vol. (mL) = 3 / 0.2 = 15 mL
Unit 14
Last update : 1/5/2014 GRAVIMETRIC ANALYSIS Subjects
Subjects
Gravimetric analysis, if methods are followed carefully, provides for exceedingly precise
analysis. In fact, gravimetric analysis was used to determine the atomic masses of many
elements to six figure accuracy. Gravimetry provides very little room for instrumental
error and does not require a series of standards for calculation of an unknown. Also,
methods often do not require expensive equipment. Gravimetric analysis, due to its high
degree of accuracy, when performed correctly, can also be used to calibrate other
instruments in place of reference standards . However , the long time needed for the
analysis makes it tedious and time consuming for this reason , the volumetric analysis
starts to overshadow gravimetry that is why we did not discuss gravimetry in more
details . Gravimetric methods have been developed for most inorganic anions and
cations, as well as for such neutral species as water, sulfurdioxide, carbon dioxide, and
iudine. A variety of organic substances can also be easily determined gravimetrically.
Unit 14
Last update : 1/5/2014 GRAVIMETRIC ANALYSIS Subjects
Subjects
Summary
In this unit we investigated the fundamentals of and the main steps in gravimetric
analysis . We also discussed the optimal conditions that produce an easily filtered and
pure precipitate . The precipitating agents have been briefly studied . The calculations
of gravimetric analysis are investigated in details with help of solved examples and
tutorial exercises . We tried to provide the student with some videos and graphs to help
him understand the main aspects of gravimetric analysis .
Last update : 1/1/2016 GRAVIMETRIC ANALYSIS
Tutorial
Exercise 1 : A 0.4960 g sample of a CaCO3 ( mw = 100) is dissolved in an acidic solution.
The calcium is precipitated as CaC2O4. H2O (mw = 146 ) and the dry precipitate is found to
weigh 0.6186 g. What is the percentage of CaO ( mw = 56 ) in the sample?
Your answer :
Our answer
next slide
GRAVIMETRIC ANALYSIS
Tutorial
Answer 1 :
Wt. CaO = Wt. of precipitate X ( mw of CaO / mw of CaC2O4.HO ) X 1
= 0.6186 X ( 56 / 146 ) X 1 = 0.237
% CaO = ( wt. CaO / wt. sample ) X 100 = ( 0.237 / 0.4960 ) X 100 = 47.78
GRAVIMETRIC ANALYSIS
Tutorial
Exercise 2 : 0.8 g sample contains sulfur S ( aw = 32 ) has been dissolved . The sulfur is
precipitated as BaSO4 ( mw = 233 ) . If the weight of the precipitate is 0.3 g calculate the
percentage of sulfur in the sample ?
Your answer :
Our answer
next slide
GRAVIMETRIC ANALYSIS
Tutorial
Answer 2 :
GRAVIMETRIC ANALYSIS
Tutorial
Exercise 3 : 644 mg of a sample contains Mg ( aw = 24 ) has been dissolved in water .
The magnesium content of the sample is precipitated as MgNH4PO4.6H2O and ignited
and weighed as Mg2P2O7 ( mw = 222 ) . If this weight is 290 mg , calculate the
percentage of Mg in the sample ?
Your answer :
Our answer
next slide
GRAVIMETRIC ANALYSIS
Tutorial
Answer 3 :
GRAVIMETRIC ANALYSIS
Tutorial
Exercise 4 : The silver content of 20 mL 0.1 M of Ag+ solution is precipitated as Ag2S
using 0.05 M solution of S2- according to the following complete reaction :
2 Ag+ + S2- Ag2S
Calculate the volume of S2- solution that is required for complete precipitation of Ag+ ?
Your answer :
Our answer
next slide
GRAVIMETRIC ANALYSIS
Tutorial
Our answer
next slide
GRAVIMETRIC ANALYSIS
Tutorial
Answer 5 :
GRAVIMETRIC ANALYSIS
Tutorial
Exercise 6 : Calculate the weight of Mn ( aw = 55 ) in 2.5 g of Mn3O4 ( mw = 229 ) ?
Your answer :
Our answer
next slide
GRAVIMETRIC ANALYSIS
Tutorial
Answer 6 :
GRAVIMETRIC ANALYSIS
Tutorial
Exercise 7 : For the determination of Zn ( aw = 65 ) gravimetricaly in a sample it is
precipitated and weighed as Zn2Fe(CN)6 ( mw = 342 ) . (1) Calculate the weight of Zn in
a sample which gives 0.35 g precipitate . (2) Calculate the weight of the precipitate which
can be produced by a sample containing 0.5 g Zn ?
Your answer :
Our answer
next slide
GRAVIMETRIC ANALYSIS
Tutorial
Answer 7 :
65
GF X 2 0.380
342
(1) Wt. of Zn 0.380 X 0.35 0.133 g
Our answer
next slide
GRAVIMETRIC ANALYSIS
Tutorial
Answer 8 :
GRAVIMETRIC ANALYSIS
Tutorial
Exercise 9 : 0.1799 g of an organic compound is burned in O2 atmosphere . The CO2
produced is collected in Ba(OH)2 solution where 0.5613 g of BaCO3 ( mw = 197 ) is
precipitated . Calculate the percentage of carbon in the organic compound ?
Your answer :
Our answer
next slide
GRAVIMETRIC ANALYSIS
Tutorial
Answer 9 :
GRAVIMETRIC ANALYSIS
Tutorial
Exercise 10 : Calculate the weight of AgI ( mw = 235 ) that can be precipitated from
0.24 g of a sample of MgI2 ( mw = 258 ) which has a purity of 30.6 %w/w ?
Your answer :
Our answer
next slide
GRAVIMETRIC ANALYSIS
Tutorial
Answer 10 :
GRAVIMETRIC ANALYSIS
Tutorial
Exercise 11 : Calculate the molar concentration of 25 mL of a solution of AgNO3 that
required to completely precipitate SCN- as AgSCN from 0.2124 g of KSCN ( mw =
89 ) ?
Your answer :
Our answer
next slide
GRAVIMETRIC ANALYSIS
Tutorial
Answer 11 :
Last update : 1/1/2016 GRAVIMETRIC ANALYSIS
Tutorial
Exercise 12 : 1.204 g of tablet containing saccharin C7H7NO3S is dissolved and the
sulphur content is oxidized to SO42- . Excess Ba(NO3)2 solution is added and the formed
BaSO4 precipitate weighed 0.5341 g .Calculate the percentage of saccharin in the tablets ?
Your answer :
Our answer
next slide
GRAVIMETRIC ANALYSIS
Tutorial
VIDEO VIDEO
You Tube Library
Last update : 1/1/2014 Page.No
على الراغبين االستماع الى محاضرات االستاذ الدكتور /ابراهيم زامل الزامل باللغة العربية عن هذا الموضوع
الرجوع الى الروابط التالية :
التحليل الوزني