Mar.

26, 2019

Calorimetry
EXPERIMENT 3: ✓It is the process of measuring the
amount of heat released or absorbed
Determination of Heat during a chemical reaction. By knowing
the change in heat, it can be
of Combustion using a determined whether or not a reaction is
exothermic or endothermic.
Bomb Calorimeter ✓Calorimetry also plays a large part of
everyday life, controlling the metabolic
rates in humans and consequently
CHE 314L: Instrumental Methods of Chemical Analysis maintaining such functions like body
Prepared by: Engr. MAAbellera temperature
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Types of Calorimetry
Types of Calorimetry
1. Constant Pressure Calorimetry
In order to measure the heat of a
2. Constant Volume (bomb)
reaction, the reaction must be isolated so calorimetry
that no heat is lost to the environment. is used to measure the heat of a
This is achieved by use of a calorimeter, reaction while holding volume
which insulates the reaction to better
contain heat. Coffee cups are often used constant and resisting large
as a quick and easy to make calorimeter amounts of pressure.
for constant pressure.

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Bomb Calorimetry
The heat of combustion at constant Bomb Calorimeter
volume of a substance containing only the
elements carbon, hydrogen, and oxygen may •A bomb calorimeter is a type of
be defined as the number of heat units constant-volume calorimeter used
liberated by the combination, in an inclosure in measuring the heat of
of constant volume, of unit mass of the
substance with oxygen to form carbon combustion of a particular reaction.
dioxide and water, the substance and the •Used to measure enthalpy changes
oxygen being initially at the same
temperature, the products of combustion of combustion reactions at a
being cooled to the initial temperature, and constant volume.
the water formed by combustion being
condensed to the liquid state.

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The Oxygen Bomb Calorimeter: The Ignition System:

The bomb calorimeter consists of three essential parts,
namely:
1) The "Bomb" or vessel in which combustion takes place.
2) The "bucket" or container holding a measured quantity of
water in which the bomb, thermocouple and stirring device
are immersed.
3) The "jacket" for protecting the bucket from the effects of
variation in room temperature, draft, etc.
Samples are ignited in the oxygen bomb by passing an electric
current through a short-length (usually 10 cm) of nickel-iron-
chromium alloy wire, a card of which is furnished with the
calorimeter.
The firing current, supplied by the ignition system is sufficient
to heat the wire yet not so high as to destroy the wire before the
sample starts to burn. A current close to 4 amperes is required to
fire the 10 cm alloy fuse.
The voltage of firing is equally important; usually a potential
drop across the 10 cm fuse is about 18 volts. The cord from the
ignition unit is attached to the calorimeter via suitable connectors
provided on the calorimeter.

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Oxygen Filling Equipment: Basically, a bomb calorimeter consists of the ff:

-Small cup to contain the sample
The oxygen filling equipment includes a cylinder of
compressed oxygen, a bench clamp for holding the bomb, which -Oxygen
serves mainly to prevent upsets when filling the bomb and for -A stainless steel bomb
preloading, and an assembly of valves, couplings, gauges and
pressure tubing. -Water
The mentioned assembly has an automatic self-sealing valve -A stirrer
to prevent back flow of the oxygen. The flow of oxygen is
controlled by a needle valve located at the front of the pressure -A thermometer
regulator. A gauge graduated from 0 to 55 atmospheres shows the -An insulator(to prevent heat flow from the
pressure to which the bomb has been charged and below it
another gauge indicates the oxygen pressure in the oxygen supply calorimeter to the surroundings)
tank. The relief valve is located underneath the pressure regulator. Ignition circuit connected to the bomb.

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Determination of Heat of Combustion in a Bomb

Determination of Heat of Combustion in a Bomb
Calorimeter
Calorimeter
• Two electrode are connected each other through platinum wire.
• The vessel is fitted with a tight screw cap. • The wire remain in a platinum dipped cap just below it.
• A small amount of substance under investigation is taken in platinum cap.
Tight screw cap

Electrode

Cap
Substance Platinum wire

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Determination of Heat of Combustion in a Bomb
Calorimeter
• It is now dipped in a insulated water bath
• which also has a mechanical stirrer and a thermometer
Water bath
Thermometer
Mechanical
stirrer
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Procedures on the Determination of Heat of
Combustion using a Bomb Calorimeter
Preliminary Operations:
1. Preparation of sample:
a) Size: For best results and for safety purposes it is
desirable to use sufficient amount of sample to produce
a temperature rise of about 2.0⁰C starting from a
temperature somewhat below room temperature.
Warning: DO NOT USE MORE THAN ONE GRAM
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Procedures on the Determination of Heat of
Combustion using a Bomb Calorimeter
2. Attaching the fuse:
Cut a single length of the fuse wire, 10 cm long, from
the provided card. Attach the wire to the electrodes A small
forceps is very helpful for this purpose. The wire must be
tightly wrapped to reduce resistance.
Attach one end of the wire to the loop electrode and
then attach the other end to the straight electrode. Bend
the wire and insert the capsule into the loop holder.
Warning: AVOID SHORTING WIRE TO CAPSULE
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Parts of a Bomb Calorimeter
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Procedures on the Determination of Heat of
Combustion using a Bomb Calorimeter
b) Pellets: It is often advantageous to compress the
sample into a pellet (by the available pellet press). The pellet
should neither be so soft it crumbles, nor so hard that it will
pop during oxidation.
The pellet is weighed to 0.1 mg in the preweighed
crucible in which it is to be burned.
The pellets should be handled with forceps or a small
pair of tongs.
Warning: DO NOT TOUCH WITH THE FINGERS
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Procedures on the Determination of Heat of
Combustion using a Bomb Calorimeter
3.The water in the bomb:
Place 1.0 ml of distilled water in the bomb from a
pipet. This amount of water serves to saturate the
oxygen as an aid in combustion and to assure that water
resulting from combustion is in the liquid state and also
to dissolve any acid formed. (Acid formation is not
expected in the case of samples used in the experiment
except for HNO3 formation, which may be found
because of the N2 in the residual air in the bomb.)
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 Mar. 26, 2019

Procedures on the Determination of Heat of Procedures on the Determination of Heat of Combustion

Combustion using a Bomb Calorimeter
4. Filling the bomb with oxygen
Observe the gauge and allow the pressure to rise slowly
until a pressure of 25-30 atmospheres is reached, then close
the control valve.
If by accident, the oxygen pressure, introduced into the
bomb, should ever exceed 30 atmospheres, DO NOT under
any circumstances, ignite the charge. The dangerously high
pressures which can be developed under such conditions
might cause the bomb to explode.
using a Bomb Calorimeter
4. The calorimeter is then placed into a vessel containing water with
agitator.
After a long enough wait for the establishment of a steady rate of
temperature change, the observations of the initial period are done.
These consist of observations over a fixed time interval, of
temperatures at equally spaced times.
At the end of the initial period, the sample is fired and
observations of temperature and time of the main period are observed
immediately.
After a steady rate of temperature change is again established, the
observations of temperature and time of the final period are made.

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Heat Capacity Heat Capacity

The heat capacity of a defined system is the
amount of heat (usually expressed in calories,
kilocalories, or joules) needed to raise the system's
temperature by one degree. To aid in the analysis
of systems having certain specific
dimensions, molar heat capacity and specific heat
capacity can be used. To measure the heat
capacity of a reaction, a calorimeter must be used.
❖Molar heat capacity- The amount of heat
needed to increase the temperature of one mole of a
substance by one degree is the molar heat capacity.
❖Specific heat capacity- The amount of heat
needed to increase the temperature of one gram of a
substance by one degree is the specific heat capacity.

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Heat of Combustion
Heat Capacity of the Calorimeter
❖Heat of Combustion
-heat released during combustion 𝜟𝑯𝒄⁰𝒔 𝒎𝒔 + 𝒆
-In particular, it is the amount of heat released when a 𝒕𝒐𝒕𝒂𝒍 𝒉𝒆𝒂𝒕 𝒄𝒂𝒑𝒂𝒄𝒊𝒕𝒚 𝑪𝒑𝒄𝒂𝒍 = ; 𝒆 = 𝒎𝒘𝒊𝒓𝒆 𝜟𝑯𝒄⁰𝒘
𝜟𝑻
given amount (usually 1 mole ) of a combustible pure
substance is burned to form incombustible products Where:
Δ𝐻𝑐𝑠⁰ = kown heat of combustion of the substance that is
Heats of combustion are used as a basis for comparing
released to the surrounding
the heating value of fuels, since the fuel that produces the
𝑚𝑠 = mass of the substance
greater amount of heat for a given cost is the more economic.
𝑚𝑤 = mass of the wire
Heats of combustion are also used in comparing the stabilities ⁰
of chemical compounds. Δ𝐻𝑐𝑤 = heat of combustion of the wire

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Heat of Combustion of the Sample
𝑪𝒑𝒄𝒂𝒍 𝜟𝑻 − 𝒎𝒘𝒊𝒓𝒆 𝜟𝑯𝒄⁰𝒘
Δ𝑯⁰𝒄 = −
𝒏 for analysis, but there are certain precautions which
Where:
Δ𝑯⁰𝒄 = heat of combustion of the substance that is
released to the surrounding
𝑪𝒑𝒄𝒂𝒍=total heat capacity of the calorimeter
𝒎𝒘 = mass of the wire
𝜟𝑯𝒄⁰𝒘 = heat of combustion of the wire
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b. Do not overcharge the bomb with too much oxygen.
The initial charging pressure should not exceed 30 atm.
c. Do not fire the bomb alone on an open bench
without providing a protective cooling medium. The bomb
should be completely submerged in water during firing.
d. Do not fire the bomb if gas bubbles are released
from any point on the bomb when it is submerged in water.
e. Do not ignite a volatile sample without using one of
the sealed sample holders.
f. Stand away from the bomb during and do not handle
the bomb for at least 6 minutes after firing.
g. Keep the bomb in good condition at all times. Any
parts that show signs of weakness or deterioration must be
replaced promptly.
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Heat of Reaction
❖ Heat of Reaction
The amount of heat that the system gives up to its
surroundings so that it can return to its initial
temperature
The heat of reaction is just the negative of the
thermal energy gained by the calorimeter and its
contents (qcalorimeter) through the combustion reaction.
−𝒒𝒓𝒙𝒏 = 𝒒𝒄𝒂𝒍𝒐𝒓𝒊𝒎𝒆𝒕𝒆𝒓
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Combustion with oxygen in a sealed bomb is a very
effective and reliable method for releasing all heat
energy obtainable from a sample and for preparing
hydrocarbon compounds and carbonaceous materials
must always be observed when using this equipment. In
particular:
a. Do not overcharge the bomb with too much
sample or with a sample which might react with
explosive violence
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Since the process takes place at constant volume, the reaction
vessel must be constructed to withstand the high pressure resulting
from the combustion process, which amounts to a confined explosion.
The vessel is usually called a “bomb”, and the technique is known
as bomb calorimetry. The reaction is initiated by discharging a capacitor
through a thin wire which ignites the mixture.
Another consequence of the constant-volume condition is that the
heat released corresponds to qv, and thus to the internal energy
change ΔU rather than to ΔH. The enthalpy change is calculated
according to the formula
ΔH=qv+(ΔngRT)
where: qv is the heat change at constant volume
Δng is the change in the number of moles of gases in the reaction.
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Heat of Reaction
where
𝒒𝒄𝒂𝒍𝒐𝒓𝒊𝒎𝒆𝒕𝒆𝒓 = 𝒒𝒃𝒐𝒎𝒃 + 𝒒𝒘𝒂𝒕𝒆𝒓
If the constant volume calorimeter is set up the same
way as before, (same steel bomb, same amount of water,
etc.) then the heat capacity of the calorimeter can be
measured using the following formula:
𝒒𝒄𝒂𝒍𝒐𝒓𝒊𝒎𝒆𝒕𝒆𝒓 = (𝒉𝒆𝒂𝒕 𝒄𝒂𝒑𝒂𝒄𝒊𝒕𝒚 𝒐𝒇 𝒄𝒂𝒍𝒐𝒓𝒊𝒎𝒆𝒕𝒆𝒓×ΔT)
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Sample Problem
A sample of biphenyl ((C6H5)2) weighing 0.526 g was
ignited in a bomb calorimeter initially at 25°C, producing a
temperature rise of 1.91 K. In a separate calibration
experiment, a sample of benzoic acid (C6H5COOH)
weighing 0.825 g was ignited under identical conditions
and produced a temperature rise of 1.94 K. For benzoic
acid, the heat of combustion at constant pressure is known
to be 3226 kJ mol–1 (that is, ΔU = –3226 kJ mol–1.) Use this
information to determine the standard enthalpy of
combustion of biphenyl.
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Sample Problem
1.150 g of sucrose goes through
combustion in a bomb calorimeter. If the
temperature rose from 23.42 °C to 27.64 °C
and the heat capacity of the calorimeter is
4.90 kJ/°C, then determine the heat of
combustion of sucrose, C12H22O11 (in kJ per
mole of C12H22O11).
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