CALORIMETRIC TECHNIQUES & CALORIC VALUE OF FOOD AND FUEL

Contents:

1. History
2. Calorimetry
3. Principle of Calorimetry
4. Calorimeter
 Parts
 Diagram
 Working & Construction
 Procedure
 Specific Heat & Latent Heat
 Calculation
5. Types of Calorimeter
6. Applications of Calorimeter
7. Calorific Value of Food
8. Calorific Value of Fuel

HISTORY:

In 1761 Black introduced the thought of heat of transformation which causes the creation of
the primary ice-calorimeters. In the year 1780, a French nobleman and chemist Lavoisier
performed an experiment in which he used the warmth form the guinea pig’s showing that
respiratory gas exchange is the combustion, almost like a candle burning.

CALORIMETRY:

The branch of Physics that deals with the measurement of heat is called Calorimetry.

PRINCIPLE OF CALORIMETRY:

 Also called Law of Mixtures.

 For an insulated system, provided there is no exchange of Heat with the surroundings,
“the heat gained by the cold body must be equal to the heat lost by the hot body”.

HEAT GAINED = HEAT LOST

10°C ⇇ 100°C

CALORIMETER:

Calorimeter is a device used for measuring the quantity of heat which may be absorbed or
released.
Parts of Calorimeter:
1. Stirrer
2. Thermometer
3. Wooden Jacket
4. Copper Vessel
5. Glass Wool [Insulating Material]

Diagram:

Working and Construction of Calorimeter:

It is a device used for measuring the quantities of heat. It consists of a

cylindrical vessel of copper provided with a stirrer. The vessel is kept inside a
wooden jacket. The space between the calorimeter and the jacket is packed with a
heat insulating material like glasswool etc., Thus the calorimeter gets thermally
isolated from the surroundings. The loss of heat due to the radiation is further by
polishing the outer surface of the calorimeter and the inner surface jacket. The lid
is provided with holes for inserting a thermometer and a stirrer into the
calorimeter.
 When bodies at different temperatures are mixed together in the Calorimeter,
Heat is exchanged between the bodies as well as with the calorimeter. If there is
no loss of heat to the surroundings, then according to the principle of Calorimetry.

Heat gained by cold bodies = Heat lost by hot bodies.

The above equation can be used to determine the Specific heat and Latent heat of
different substances.

Procedure of Calorimeter:

Now let us find the enthalpy change per mole of a substance A in a reaction
between two substances A and B. Here, both the substances A and B, are
separately added to a calorimeter and the initial and final temperature (before the
reaction has started and it’s finished are noted. Multiplying the natural process by
mass and heat capacities of the substances gives worth for the energy given off or
absorbed during the reaction. Dividing the energy change by what percentage
.moles of A were present gives its enthalpy change of the reaction.

q = Cv (Tf - Ti)q = Cv (Tf - Ti)

Where q is that the amount of warmth consistent with the change in temperature
measured in joules and Cv is that the heat capacity of the calorimeter which is
measured in units of energy per temperature (Joules/Kelvin).

SPECIFIC HEAT (C):

The quantity of heat required to raise the temperature of 1g of a substance by 1

Celsius degree.

Unit of Specific heat, usually calories (or) joules per gram per celsius degree (I/g/
°C)

Q= mCΔT

LATENT HEAT (L):

Also called Latent energy (or) heat of transformation. Latent heat is energy
released or absorbed by a body or a thermodynamic system during a constant
temperature process.

It express the amount of energy in the form of heat (Q) required to completely
effect a phase change of a unit of mass (m) usually 1 kg of a substance as an
Intensive property.

L = Q (Heat) / M (Mass)
 CALCULATION:

A B

TA = 100°C TB = 20°C
(Metal) (Water)

Let us consider two objects namely A & B with a initial temperature 100°C & 20°C
respectively.

After sometimes, we can say by using Calorimetric techniques,

Heat Gained by the Object B = Heat lost by the object A

Qgain = - Qloss

mBCB Δ TB = - mACA Δ TA

mBCB (Tf – TB) = - mACA (Tf – TA)

mBCB Tf - mBCB TB = - mACATf + mACATA

mBCB Tf + mACATf = mACATA + mBCB TB

Tf (mBCB + mACA) = mACATA + mBCB TB

Tf = mACATA + mBCB TB
mACA+ mBCB

TA – Initial temperature of Metal

CA – Specific heat of Metal

mA – mass of Metal

Tf - Final temperature of both Metal & Water are same

TB – Initial Temperature of Water

CB – Specific heat of Water

mB – Mass of Water
TYPES OF CALORIMETER:

Adiabatic Calorimeters

An adiabatic calorimeter is a calorimeter which helps to examine a runaway reaction. As a

result of an adiabatic environment, any heat generated by the fabric sample under test causes
the sample to extend in temperature, thus fuelling the reaction. The adiabatic calorimeter is
actually a wrong term because it’s not fully adiabatic. Some amount of heat is usually lost by
the sample to the sample holder. A mathematical correction factor, referred to as the phi-
factor, are often wont to adjust the calorimetric result to account for these heat losses.

Reaction Calorimeters

A reaction calorimeter may be a calorimeter during which a reaction is initiated within a

closed insulated container. Reaction heats are measured and therefore the heat content is
obtained by integrating heat flow versus time. This is the quality utilized in industry to live
heats since industrial processes are engineered to run at constant temperatures.

There are four primary types of methods for measuring the warmth in reaction calorimeter:

1) Heat Flow Calorimeter - The cooling/heating jacket plays an important role in

controlling either the temperature of the method or the temperature of the jacket. Heat
is measured by monitoring the temperature difference between hem transfer fluid and
therefore the process fluid.
2) Heat Balance Calorimeter - The cooling/heating Jacket controls the temperature of the
method. Heat is measured by monitoring the warmth gained or lost by the warmth
transfer fluid.
3) Power Compensation - Power compensation uses a heater placed within the vessel to take
care of a continuing temperature. The energy supplied to the present heater is often varied as
reactions require ,and therefore the calorimetry signal is only derived from this electric power.
4) Constant Flux Calorimeter - Constant flux calorimetry (or COfLUX) springs from
heat balance calorimetry and uses specialized control mechanisms to take care of a
continuing heat flow (or flux) across the vessel wall.

Bomb Calorimeters

A bomb may be a sort of constant-volume calorimeter utilized in measuring the warmth of

combustion of a specific reaction. Electrical energy is employed to ignite the fuel; because
the fuel is burning, it’ll hear up the encompassing air, which expands and escapes through a
tube that leads the air out of the calorimeter.When the air is escaping through the copper tube
it’ll also heat up the water outside the tube. The temperature difference of the water allows
for calculating the calorie content of the fuel.

In brief, a bomb consists of a little cup to contain the sample, oxygen a chrome steel bomb,
water, a stirrer, a thermometer, the dewar or insulating container (to prevent heat be due to
the calorimeter to the surroundings) and ignition circuit connected to the bomb. By using
chrome steel for the bomb, the reaction will occur with no volume change observed.

Calvet-type Calorimeters

The detection is predicated on a three-dimensional fluxmeter sensor. The fluxmeter element

consists of a hoop of several thermocouples serial The alternative thermopile having high
thermal conductivity surrounds the experimental space within the calorimetric block. The
thermopiles arranged radially guarantees an almost complete integration of the warmth. The
calibration of the calorimetric detectors may be a key parameter and has got to be performed
very carefully. For this Calve-type calorimeters. a selected calibration, named as Joule effect
or electrical calibration, has been developed and used to beat all sorts of issues.

The main advantages of this son of calibration are as follows:

1) It is an absolute calibration.
2) The use of standard materials for calibration is not necessary. The calibration is often
performed at a continuing temperature, within the heating mode and within the
cooling mode.
3) It can be applied to any experimental vessel volume.
4) It is a very accurate calibration.

Adiabatic Calorimeters

Adiabatic calorimeters measure the change the enthalpy of a reaction occurring in solution.
During the reaction, the no heat exchange with the surroundings is allowed and the
atmospheric pressure remains constant.

Differential Scanning Calorimeter

In this differential scanning calorimeter or DSC. heat flows into a sample which ls usually
contained within a small aluminium capsule or 'pan·. This heat flow Is measured
differentially. i.e. .. by comparing It to the flow into an empty reference pan.

Isothermal Titration Calorimeter

In an isothermal titration calorimeter. the warmth of reaction is employed to follow a titration

experiment. This technique is gaining high importance mainly, within the field of
biochemistry because it facilitates the determination of substrate binding to enzymes. The
technique is usually utilized in the pharmaceutical industry to characterize potential drug
candidates.
FAQs About Calorimeter

Q.1. What is the working principle of a calorimeter ?

Answer – The working principle of calorimetry states that in the case of an insulated system,
the heat energy lost by the hot body is equal to the heat energy lost by the hot body is equal to
the energy gained by the cold body. On a note; Heat transfer continues until both the bodies
attain the same temperature (t).

Q.2. Why Copper is used in the calorimeter ?

Answer – First of all, Cu is a good conductor of heat. Secondly, as Cu has low SHC it reaches
the equilibrium temperature quickly by absorbing a small amount of heat. This makes sure
calorimeter absorbs or liberates a small amount of heat during the heat exchange.

Q.3. How does a coffee cup calorimeter work ?

Answer - The cup is partially filled with a known volume of water and a sensitive
thermometer is inserted through the lid of the cup so that its bulb is below the water surface.
Whenever a chemical reaction takes place in the coffee cup calorimeter, the water absorbs the
heat of the reaction.
APPLICATIONS

The following are some of the key application areas of calorimeters:

 In biochemistry/chemistry labs
 In thermodynamics study
 In the study of different materials, such as nanomaterials, zeolites and ceramics
 For assessing the thermal hazard potential of Li batteries
 For examining polymeric materials to determine their thermal transitions
 In solid and liquid fuel testing
 Waste and refuse disposal
 In the study of liquid crystals
 In the pharmaceutical and polymer industries
 To observe fusion and crystallization events and glass transition temperatures
 Food and metabolic studies
 For propellant and explosive testing
 In educational training
 Differential scanning calorimeters are used to find the change In any product's
formula and Its effects
 A reaction calorimeter is used to measure the heat generated by the sensors in
reactors.
 A constant pressure calorimeter helps us to measure the enthalpy change in both
physical and chemical methods.
 The adiabatic calorimeter is used to evaluate the runtime reactions.
 Bomb calorimeters are widely used in different kinds or fields. Some of the fields are
analysis of waste products, manufacture or cement, analysis of fuel like coal and
explosives, food and nutrition, research in animal feed and so on. For example, the
Oxygen bomb calorimeter has its usage in the field of food testing by calculating the
amount of heat in food which further helps to determine the calorie or the food.
 Pharmaceutical calorimeters allow drug developers to verify the point at which a drug
might become crystallized or unstable, which is especially useful in the final
development of amorphous drug compounds.

CALORIFIC VALUE:

Calorific Value Definition

"Calorific value refers to the amount of heat produced by unit volume of a substance by
complete combustion."
What is the Calorific value?

Calorific value is the amount of heat energy present in food or fuel and which is determined
by the complete combustion of specified quantity at constant pressure and in normal
conditions. It is also called calorific power. The unit of calorific value is kilojoule per
kilogram i.e. KJ/Kg.

Water vapour is generated in the combustion process and the heat should be recovered by
using certain techniques. If the heat contained in the water vapour could be recovered then it
has high calorific value. If heat contained in the water vapor could not be recovered when it
has low calorific value.

The efficiency of fuel or food mainly depends on the calorific value. If the value is high, its
efficiency will also be high. If the value is low, its efficiency would also decrease. Calorific
value is directly proportional to its efficiency.

A detailed list of foods and their calorific values:

The calorific value of food indicates the total amount of energy, a human body could generate
during its metabolism which is expressed in Kilojoules per 100 grams or 100 ml. The
calorific value of food is generally expressed in kilocalories i.e. kcal. The below table shows
the type of food and its calorific value:

Calorific Value (Approximately)

Category of food Quantity (Grams)
Kilojoules (KJ) Kilocalories (Kcal)

Dietary fibre 1 8 2

Polyhydric Alcohols 1 10 2.4

Alcohols 1 29 7

Carbohydrates 1 17 4

Protein 1 17 4

Fats 1 37 9

Fats have more calorific value when compared to carbohydrates, protein, alcohols, roughage
and other biomolecules involved in the maintenance and metabolic processes.
CALORIFIC VALUE OF A FUEL. HOW IT IS CALCULATED. EXPLAIN WITH
EXAMPLE.

Calorific Value

Calorific value may be defined as the amounr of heat liberated in calories by the complete
combustion of a combustible material with oxygen and the condensation of the products to
the desired temperature.

Consider, the combustion of carbon and hydrogen, which may be represented by the
following equations.
C + O2 → CO2 + 97,644 Cals
12 gms 32 gms 44 gms

H2 + O → H2O + 69,000 Cals

Calorific Value of Fuel

Here is the detailed list of fuels and their calorific values:

Fuel Calorific Value of Fuel

(Approximately)

Cow Dung 8000

Wood 22000

Coal 33000

Biogas 40000

Diesel 45000

Kerosene 45000

Petrol 45000

Methane 50000

LPG 55000

LPG has more calorific value when compared to diesel, petrol, and kerosene.
Importance of Calorific Value

It is very important to have a knowledge of the calorific value of fuel to carry out our day-to-
day activities. This knowledge helps us to determine the amount of energy we transport. The
gas shippers and suppliers require this information to bill gas consumers. It also helps to
determine transportation charges of gas shippers and suppliers.

The human body requires calories to carry out daily activities. Without calories, the body
would stop working and the cells i111 the body would die. But, if people consumed only a
specific amount of calories each day, they would lead a healthy life. Too high or too low
calorie consumption eventually leads to health problems.

Reference Book - New Simplified Physics by Author: S.L Arora

Reference Websites

 https://www.toppr.com/guides/physics/heat/calorimeter/
 https://byjus.com/physics/calorimeter/
 https://en.wikipedia.org/wiki/Calorimeter