Thermochemistry

 Thermochemistry is the branch of physical chemistry which deals with

the thermal changes accompanying chemical and physical
transformation.
 Its aim are the determination of the quantity of energy emitted or
absorbed as heat in various processes, as well as the development of
method for calculating these thermal readjustments without recourse
to experiment.
 Thermochemistry focuses on these energy changes, particularly on the
system's energy exchange with its a surroundings.
 Thermochemistry is useful in predicting reactant and product quantities
throughout the course of a given reaction.
 In combination with entropy determinations, it is also used to predict
whether a reaction is spontaneous or non-spontaneous, favorable or
unfavorable.
 Form the practical point of view it is essential to know whether heat is
evolved or absorbed in a particular reaction.
 It is imperative to consider how heats of reaction are determined
experimentally, as well as some of the method and principles that have
been deduce from thermodynamics for evaluation of such thermal
changes without appeal to experiment in each case.
 The subject matter of the thermochemistry is based on the first law of
thermodynamics.
 Thermochemistry provides important information regarding bond
energies, heat of combustion, heat of neutralization and heat of
formation etc.
Several thermodynamic definitions are very useful in thermochemistry. A system is the specific portion
of the universe that is being studied. Everything outside the system is considered the surroundings or
environment. A system may be:
 a (completely) isolated system which can exchange neither energy nor matter with the surroundings,
such as an insulated bomb calorimeter
 a thermally isolated system which can exchange mechanical work but not heat or matter, such as an
insulated closed piston or balloon
 a mechanically isolated system which can exchange heat but not mechanical work or matter, such
as an uninsulated bomb calorimeter
 a closed system which can exchange energy but not matter, such as an uninsulated closed piston or
balloon
 an open system which it can exchange both matter and energy with the surroundings, such as a pot
of boiling water
 A system undergoes a process when one or more of its properties changes. A process relates to the
change of state. An isothermal (same-temperature) process occurs when temperature of the system
remains constant. An isobaric (same-pressure) process occurs when the pressure of the system
remains constant. A process is adiabatic when no heat exchange occurs.
First law of thermodynamics (Conservation of energy):
The first law of the thermodynamics is the law of conservation of energy. Energy may be transformed
from one form into another form; it can neither be created nor destroyed. In other words whenever
energy of a particular form disappear an exactly equivalent amount of another form must be
produced. According to the first law “the total energy of a system and its surroundings are conversed”.
Gain or loss in energy by the system is exactly compensated by the loss or gain in energy of the
surroundings. The law is universally valid for all process.
If we let E be the increase in the internal energy of the system and W be the work
done by the system on its surroundings, then by first law
E  W  q ;  E  q  W
Consider a cylinder, cross-sectional area = A, p is the pressure on piston. Pressure is
force per unit area
f
p
A Where f = force.
 f  pA
 dv  Adl
dw  fdl  pAdl
dw  pdv
v2
w pdv  p(v 2  v1 )  pv
v1

E  q  W  q  pv
Energy: Energy is defined as the capacity to do work. Every system
containing some quantity of matter possesses a store of energy. It may
occurs in various forms such as kinetic energy due to the motion of the
body, molecules or atoms, potential energy by virtue of its position, thermal
energy due to the temperature of the body, chemical energy due to the
constitution of the compounds, nuclear energy and mechanical energy etc.
Energy is stored in the molecules and its release can be used to
produce heat Energy transformation:
a)Chemical to Electrical (storage battery, Dry cell)
b)Chemical to Thermal (Home furnace)
c) Chemical to Kinetic (rockets, jet engine)
d)Electrical to Mechanical (Electrical motor)
e)Electrical to radiant (fluorescent lamp)
f) Potential to mechanical(Hydraulic turbine)
 The energy possessed by a system due to translational, vibrational and rotational
motions of molecules, atoms or ions along with the energy of the electron and the
nuclei is known as its internal or intrinsic energy or energy contain of the system.
 Internal energy = Potential energy + kinetic energy.
 The energy acquired by a system in forced field like electrical, magnetic and
gravitational are termed as external energies and are not considered as part of the
internal energy of the system.
 The energy contain of a system is denoted by E and depends on the internal
structure and the constitution of the material composing the system. It is
independent of the previous history of the system, the magnitude of the energy is
determine by system and in turn by the variable of the system like pressure, volume
and temperature.
 As these variables are related to one another by an equation of state, the energy of
the system of fixed composition may be described in term of any two of their state
variables i.e.
E  f1 ( p, t )  f 2 (v, t )  f 3 ( p, v)
If in the transformation the system changes from state A to some other state B, the
energy change E  EB  E A
is determined by the value of variables in the two states. The change in the state of the
system can be brought about by a number of the path but the change in E is always
same. Energy is therefore a state function. In a cyclic process the initial state of the
system is restored and the energy change would be zero.
Energy is an extensive property i.e. its magnitude depends upon the quantity of
materials in the system. The facts can be stated mathematically as
1) Energy is a state function
2) dE is an exact differential
3)  dE  0
4) Internal energy is extensive property.
The enthalpy of a system
Thermal change at constant pressure is most conveniently expressed in term of
another function, H called the Enthalpy or heat content of a system.
H = E+PV where p and v are the pressure and volume of the system. H is also a
function of the state of the system and is completely independent of the manner in
which the state is achieved. Consequently the change in enthalpy ,∆ H may be written
as
∆H = H2-H1 where H2 is the enthalpy the system in the final state and H1 the enthalpy
in the initial state.

H 1  E1  p1v1
andH 2  E 2  p 2 v 2
   H 2  H 1  ( E 2  p 2 v 2 )  ( E1  p1v1 )
 E 2  E1  p 2 v 2  p1v1
 E  pv
The change in enthalpy at constant pressure is equal to the increase in
internal energy plus pressure volume work done. Hence at constant
pressure ∆H is the heat absorbed by a system going from an initial state
to a final state provided the only work done is P-V works.
(Heat absorbed at constant pressure) = (change in internal energy) +
(work done on surroundings)
Heat of reaction at constant volume or pressure:
 There are two general conditions under which thermochemical measurements are
made (a) constant volume and (b) constant pressure.
 The magnitudes of the thermal changes obtained under these two conditions are, in
general, different.
 At constant volume any thermal change taking place must be done only to the
difference in the sum of the internal energy of the product and the sum of the
internal energy of the reactants.
 At constant pressure, however, not only does the change in the internal energy take
place, but work is also involved.
 The exact significance of both types of measurement can best be obtained by
applying the first law of thermodynamics to the thermal change occurring within
colorimeter.

 According to the first law, any heat q added to the system will in general go to
increase the internal energy of the system and perform external work, namely
v2
q  E  W  E   pdv
v1
That is any thermal change occurring in the calorimeter at constant volume must be
changed in the internal energy due to the chemical reaction or physical transformation.

On the other hand, when the pressure kept constant i.e. the system is either open to the
atmosphere or confined within a vessel on which a constant external pressure is exerted.
q p    E  W  E  pv …….. (3)
v2
W  pdv  p(v 2  v1 )  pv
v1

Under these conditions, the volume of the system will be changed. The thermal change at
constant pressure not only involves the change in the internal energy of the system but also
work performed either in expansion or in contraction of the system,
q p  E  pv  E p  E r  p(v p  v r )  E p  pv p  ( E r  pv r )  H p  H r  
Where the subscript p and r refer to products and reactants respectively.
Relation between E and H :

According to the equation H  E  pv , the difference between H and E is given

by pv where p is constant. The significant factor determining the difference is, therefore
v the change in volume which occurs during reaction. For reactions involving solids and
liquid only, H is equal to E since the volume change are usually very slight. In reaction
involving gases, however, the volume may be large. If in general we have a reaction in
which are involved nr moles of gaseous reactants and n p moles of gaseous products.
pvr  nr RT and pv p  n p RT and since pressure is constant
p v  p ( v p  v r )
H  E  pv
 (n p  n r ) RT
 E  n g RT
 n g RT
(Subscript g is for gas)
What do you mean by the equation E =q+W... (1)

Ans: The change of internal energy E of a system is the sum of the heat q and W added
to the system. If the values of q in equation is positive, heat flows into the system from the
surrounding. If the value of W is +ve, work is done on the system by forcing the volume
of the system to decrease.
*Thus, the internal energy change of a system that gives 50 j of heat and has 5 j of work
done on it by the surroundings is E = (50+5) j=55 j
*If the value of q is negative the system loses heat to the surroundings. If the value of w is
negative the system does work on the surroundings. For example, a system can do work by
expending against the external pressure. When the volume of the system increase the
system does work on the surrounding.
* A system absorbs heat 1000 j from the surroundings and does 2 j of work on the
surroundings. What is E for the system and for the surroundings?
E  q  W  1000 j  (2 j )  998 j
Change in enthalpy = change in internal energy + work done on surroundings
i.e. the change in enthalpy is equal to the heat absorbed at constant pressure.
If v is +ve, as in an expansion,   E
If v is –ve, as in a contraction   E
If v is 0, i.e. in rection at constant volume,   E
Factors that affect enthalpy change:
The enthalpy change for a reaction depends on the conditions under which the
reaction occurs. The affects of various conditions on enthalpy change are discussed
below:
1) The enthalpy change of a reaction is an extensive property of the system i.e. it
depend on the quantities of reactant and products.
2. The enthalpy change for a reaction written form “left to right” is equal in magnitude
but opposite in sign to the enthalpy change for reverse reaction.

3. The enthalpy change for the reaction depends on the physical states of the reactant
and products.
1 1
I 2( g )  H 2( g )  HI ( g ) ;   36.5kj
2 2

1 1
I 2( s )  H 2( g )  HI ( g ) ;   25.9kj
2 2 1 1
I 2 ( s )  I 2( g ) ;   62.4kj
2 2
4. The enthalpy change for a reaction depends on the temperature and pressure. The
condition of 1 atm and 298k referred to as standard condition
Thermo chemical laws: The two important law of thermochemistry are based on the
principle of conservation of energy.
(1)Lavoisier and Laplace law: The quantity of heat required for the decomposition of
a compound into its elements must be equal to the heat evolved during the formation
of the compounds from its elements. The importance of this law is that the
thermochemical equations can be reversed, provided the sign of ∆H is changed.

1 1
H 2 ( g )  Cl 2 ( g )  HCl ( g ) ;  0  92.31kj
2 2
1 1
HCl ( g )  H 2 ( g )  Cl 2 ( g ) ;  0  92.31kj
2 2
2) Germain Henri Hess (a Swiss-born Russian chemist 1802-1850)
Hess’s law of heat summation: This law states that the total enthalpy
change for a reaction is the same whether the reaction takes place in a
single step or in several steps.
The thermochemistry aspect of this law is that the enthalpy is a state
function and so depends on the initial and final states of the reacting
system and is independent of the path connecting them.
If a reaction occurs in two or more steps, the enthalpy for the reaction is
the sum of the enthalpies of the individual steps.
This is known as Hess’s law of heat summation. If a reaction can take
place by more than one route the overall change in enthalpy is the same,
whichever route is followed.
One results of Hess’s law is that the thermochemical equation can be treated as
simple algebraic equation which can be added, subtracted multiplied or divided by an
integer. With the help of this law enthalpy change can be calculated for reactions in
which direct experimental measurements are difficult. Suppose it is desired to find ∆H
for the reaction. 2C( s )  2 H 2( g )  O2( g )  CH 3COOH (l ) ;  25 c  ?
0

The heat of this reaction could not be determined directly. However calorimeter
measurements are available for the reactions.
(1)CH 3COOH (l )  2O2( g )  2CO2( g )  2 H 2 O(l ) ; H 250 c  20834 0 0cal
(2)C ( s )  O2( g )  CO2( g ) ; H 250 c  94050cal
1
(3) H 2( g )  O2( g )  H 2 O(l ) ; H 250 c  68320cal
2
If we now multiply equation 2 and equation 3 by 2 and then add we have
2C( s )  2O2( g )  2CO2( g ) ; H 250 c  188100cal
2 H 2( g )  O2( g )  2 H 2 O(l ) ; H 250 c  136640cal
(4)2C ( s )  2 H 2( g )  3O2( g )  2CO2  2 H 2 O(l ) ;  250 c  324740cal
Now on subtraction of equation 1 from equation 4 we obtained

2C ( s )  2 H 2 ( g )  O2( g )  CH 3COOH (l ) ;  250 c  116400cal

Enthalpy of formation

The enthalpy change observed when one mole of a compound in its standard state
forms from its elements in their standard state at 1 atm and 298K is called the standard
molar enthalpy of formation, denoted by ∆H0f. The enthalpy change for any reaction is
∆ H = Hproducts – H reactants ……………….. eqn( 1 )
Let us consider the formation of a mole of O2 gas form the same element O(g) :
2 O ( g ) = O2 ( g ). The initial and final state are identical, their enthalpies are equal,
and according to eqn (1) ∆H is zero. ∆H = H2O(g) – HO2(g) = 0. Therefore, the standard
enthalpy of formation of an element in its standard state is zero.
Enthalpy of formation provides us with information about the stabilities of compound
relative to their elements. The word “stability” here means thermodynamics stability. If
the standard enthalpy of formation of a compound is highly exothermic, the reverse
reaction, thermal decomposition of the compound will be highly endothermic.
The enthalpy change for a chemical reaction equals the sum of the enthalpy of
formation of all the products, minus the sum of the enthalpy of formation of all the
reactants H 0  H 0  H 0
xyn f ( product) f ( reac tan t )
Calculate the standard enthalpy change for the photosynthesis reaction in which plants
convert carbon dioxide and water to the glucose C6H12O6 (s) and oxygen gas. Is this
reaction is exothermic or endothermic?

Solution
The balanced equation for the reaction:

6CO2 ( g ) + 6H2O ( l ) = C6H12O6 = 6O2 ( g )

we know
H r0n  H 0f ( product)  H 0f ( react )

H r0n  H 0f of C 6 H 12O6  6H 0f of O2 ( g )  6H 0f of CO2 ( g )  6H 0f of H 2 O

 [(1mol)( 1260 KJ / mol)  0]  [(6mol)( 394 KJ / mol)  (6mol)( 286 KJ / mol)]

 2820 KJ
the enthalpy required to drive the synthesis of glucose from carbon dioxide and water is
provided by light.
Heat of neutralization of acid and base:
When dilute solution of strong acid are neutralized with dilute solution of strong base
at room temperature, the heat of neutralization per mole of water formed is essentially
constant and independent of the nature of the acid or base.
H+ ( a = 1 ) + OH- ( a = 1 ) = H2O (l) ∆H025C = -13360 cal
HCN + OH- = H2O(l) ∆H025C = 2460 cal
HCN = H+ + CN- ∆H025C = ∆H01
H+ + OH- = H2O(l) ∆H025C = 13360 cal

HCN + OH- = CN- + H2O

∆H025C = ∆H01 – 13360 cal
∆H01 = ∆H025C + 13360cal
= -2460 + 13360
= 10900 cal

1. NH4OH ( aq ) + H+ (aq) = NH4+ ( aq ) + H2O (l) ∆H0 = -5146 KJ / mol

2. H+ (aq) + OH- (aq) =H2O (l) ∆H0 = -57.32 KJ / mole

3. NH4OH (aq) = NH4+ (aq) + OH- (aq) ∆H0 = ∆H ionization

Adding (2) & (3)

-57.32 + ∆H0i = ∆H025C = - 51.46 KJ

∆H0i = 57.32 – 51.46 = 5.861 KJ

Problem:
a) When 100g of H2O at 94.00C were added to a calorimeter at 17.50C the temp rise
to 80.50C
b) 250 cm3 of NaOH (0.4 M) were added to 250cm3 of HCl acid (0.4 M) in the
calorimeter. The temp of the two solutions was 17.50C initially and rise to 20.10C.
Calculate the enthalpy of neutralization.

Answer:

The assumption is made that specific heat capacity of the solution are the same as that of
water, 4180 Jkg-1K-1
In a) heat given out by water = heat received by calorimeter of
=0.100 × 4180 ( 94 – 80.5 ) = C ( 80.5– 17.5) C = 90 JK-1

In ( b ) Heat from neutralization = Heat received by calorimeter + solution

=90(20.1 – 17.5) + ( 0.5 × 4180 ) ( 20.1 – 17.5)
= 5670 J
Amount of water formed = 250 × 10-3 × 0 .40
= 0.100 mol
Heat evolved per mole = 5670/0.1 = 56700 J
The standard enthalpy of neutralization is 56.7 kJ/mole
Heat of combustion:
The terms heat of combustion refers to the amount of heat liberate per mole of
substance burned. The heat evolved in the complete combustion of many organic
compounds in oxygen has been carefully determined. The method ordinarily used is to
burn the substance in a combustion bomb and to measure the heat evolved. Heat of
combustion may be employed directly to calculate heats of formation of organic
compounds. Enthalpies of combustion are used for determining the calorific value of
foods and fuels, estimating the flame temperature, bond energies and in deciding the
constitution of isomeric substances.
For gaseous propane, the heat of combustion is
C3H8(g) + 5O2(g) = 3CO2 + 4H2O(l) ∆H025C = - 530610 cal
∆H025C = ( ∆Hco2 + 4∆HH20 ) – (∆HC3H8(g) + 5∆HO2 )
-530610 = 3 x ( -94050 ) + 4x ( -68320 ) - ∆HC3H8 + 0
∆HC3H8 = - 282150 – 273280 + 530610
= - 555430 + 530610
= -24820 cal / mol

C(diamond) + O2(g) = CO2(g) ∆H025C = - 94500 cal

C graphite  O2( g )  CO2 ;  250 c  94050cal; C grap  Cdia ;  025  450cal
Heat of solution and dilution:

Solution of one substance in another is accompanied by absorption or evolution of heat,

and this thermal effect is termed the integral heat of solution of the substance. Per mole
of dissolved substance the integral heat of solution at any given temperature and
pressure depends upon the amount solvent in which solution takes place. For this
reason it is essential to specify the number of moles of solvent per mole of solute in
giving a heat of solution, as

H2SO4 (l) + 10H2O = H2SO4 ( 10H2O ) ∆H25C = -16240 cal

H2SO4 (l) + aq = H2SO4 (aq ) ∆H25C = -22990 cal

The change in enthalpy when a solution form one specified concentration is diluted to
some other specified concentration is called the integral enthalpy of dilution. The
difference between any two integral heat of solution gives the heat evolved in dilution of
a substance form the initial state to final state, and it is termed the integral heat of
dilution of the substance.
H 2 SO4 (2 H 2 O)  8H 2 O(l )  H 2 SO4 (10 H 2 O);  250 c  ?
H 2 SO4  10 H 2 O  H 2 SO4 (10 H 2 O);   16240cal
H 2 SO4  2 H 2 O  H 2 SO4 (2 H 2 O);   9960cal
10 2 O  2 H 2 O  H 2 SO4 (10 H 2 O)  H 2 SO4 (2 H 2 O);  250 c  16240  (9960)cal
H 2 SO4 (2 H 2 O)  8H 2 O  H 2 SO4 (10 H 2 O);  250 c  16240  9960  6280cal
H 2 SO4 (2 H 2 O)  aq  H 2 SO4 (aq);  250 c  22990  (9960)
 13030cal
 The differential enthalpy of a solution is defined as the enthalpy change when one
mole of a solute is added to such a large amount of the solution that its concentration
does not change appreciably. It is also known as the partial molar enthalpy of the
solution
 The enthalpy change accompanying the addition of a mole of a solvent to a large
volume of the solution without effecting the concentration of the solution is referred to
as the differential enthalpy of dilution or partial molar enthalpy of dilution.
Variation of heat of reaction with temperature:

In general ∆H of a reaction is a function of temperature and pressure, and ∆E is a

function of temperature and volume. We shall consider here only the effects of
temperature on ∆H and ∆E

The heat of reaction obtained calorimetrically or by calculation corresponds to some at

definite temperature. At other temperature the heat of the reaction will usually not be
same. As reactions are carried out at various temperatures, it is very frequently
necessary to know heat of reaction at temperature other than those at which they were
determined. A method of calculating the heat of reaction at one temperature from that at
another is, therefore highly desirable.

In such calculation heat capacity play a very important role, we have seen that these
are two types of heat capacities, Cp and Cv.
Heat capacity: Consider a very small quantity of heat dq added to a system, and
suppose that as a result of the heat absorption the temperature rise produced is dT. Then
dq
the amount of heat required to raise temperature of the system 1 degree is C  and
dT
thus C is the heat capacity of the system. Now From equation

dq  dE  pdv
dE  pdv
c  dq dE  pdv
dT  ....(1)
dT dT

dq
Since C
dT
 dE 
Cv    When the volume is held constant. So, dv=0
 dT  v

Cv is the rate of change of the internal energy with temperature at constant volume.
When the heat of absorption occurs reversibly at constant pressure, then from equation 1
 dE   dv 
Cp     p 
 dT  p  dT  p
But if equation H = E + PV be differentiated with respect to T at constant P, we get
 dH   dE   dv 
      p    Cp
 dT  p  dT  p  dT  p
 dH 
C p   
 dT  p
Therefore, Cp is the rate of change of enthalpy with temperature at constant pressure.
The differential equation for the variation of heat of reaction with temperature may be
obtained as follows since differentiating of    p   r , with respect to absolute
 d ()   dH p   dH r 
temperature at constant pressure yields   
 
   the second and
 dT  p  dT  p  dT  p
third terms are Cp ( prod) and Cp ( react ) respectively
 d () 
 dT   C p ( product)  C p ( react )  C p .........(1)
p
In the same manner, we obtained
 d (E ) 
 dT   Cv ( product)  CV ( react)  Cv ……….. (2)
v

 d (H ) 
The integration of    Cp depends on whether C p is constant or temperature
 dT  p
dependent. When C p is constant, then integration between two temperature T1 and T2
yields.
 2 T2
1
d ()   C p dT . Where  1 is the heat of reaction at T1 and  2 that at T2
T1

temperature.
T2
 2  1  C p  dT  C p (T2  T1 )
T1

  2  1  C p (T2  T1 ).....................(3)

When C p is not constant but variable with temperature, the variation is generally
expressed by empirical formula of the type C p  a  bT  cT 2  dT 3  ......... Where a, b,
c, and d are constant for a given substance.  d ()  C p dT   0 , where 0 is the
integration constant.
   C p dT  0 ………..(4)
on the other hand
 2 T2 T2
1
d ()  
T1
C p dT   (a  bT  cT 2  dT 3  .....)wherea  a p  a r
T1

T2  T1 T2  T1
2 2 3 3

 2  1  a(T2  T1 )  b( )  c( )  ........

2 3
Example: Suppose it is desired to calculate at 348 0 k for the reaction
1 1
H 2( g )  Cl2 ( g )  HCl ( g ) ;  02950 k  22060cal
2 2
The mean heat capacity over this temperature interval is:
C p  C p ( product)  C p ( reac tan t )
 2( g ) : C p  6.82calmol 1 deg 1 1 1
1 1
 6.81   6.82   7.7
Cl2( g ) : C p  7.71calmol deg 2 2
 0.46
 Cl( g ) : C p  6.81calmol 1 deg 1
 2   1  C p (T2  T1 )
 348
0
0
k
 22060  (0.46)(348  298)
 22080cal
Enthalpy changes and Bond Energies:
When a chemical reaction is exothermic the products are more stable than the
reactants. During the course of a chemical reaction of molecular compound, the bonds
between the atoms of the reactant molecules break and the atoms rearrange to form
new bond in the product molecules. In the exothermic reaction the products have
stronger bond or more bonds than the reactants.
The bond energy is defined as the energy required to break a bond. Since energy is
required to break a bond, energy is released when a bond is formed.
H2 (g) → H (g) + H (g); ∆H0 = 436 KJ

2 H (g) → H2 (g) ; ∆H0 = -436 KJ

Cl2 = 2 Cl ; ∆H0 = 244 KJ

H (g) + Cl (g) → HCl (g); ∆H0 = - 432KJ

1/2 H2 (g)  H (g); ∆H0 = 218 KJ

1/2 Cl2 (g)  Cl (g); ∆H0 = 122 KJ

∆H0r × h = (218 +122 -432) KJ

= -92 KJ

For any chemical reaction, the enthalpy change is the sum of all the bond energies of the
reactants minus sum of the all bond energies of the products.

∆H0r × h = (BE of reactant) - (BE of products)

A calorimeter is an object used for the process of measuring the heat of chemical
reactions or physical changes as well as heat capacity. Differential scanning
calorimeters, isothermal micro calorimeters, titration calorimeters and accelerated rate
calorimeters are among the most common types. A simple calorimeter just consists of
a thermometer attached to a metal container full of water suspended above a
combustion chamber. It is one of the measurement devices used in the study of
thermodynamics, chemistry, and biochemistry.
Bomb calorimeter:
A bomb calorimeter is a type of constant-volume calorimeter used in measuring the
heat of combustion of a particular reaction. Bomb calorimeters have to withstand the
large pressure within the calorimeter as the reaction is being measured. Electrical
energy is used to ignite the fuel; as the fuel is burning, it will heat up the surrounding
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 will also heat up the
water outside the tube. The change in temperature of the water allows for calculating
calorie content of the fuel.
The bomb, with the known mass of the sample and oxygen, form a closed system — no
gases escape during the reaction. The weighed reactant put inside the steel container is
then ignited.
Energy is released by the combustion and heat flow from this crosses the stainless steel
wall, thus raising the temperature of the steel bomb, its contents, and the surrounding
water jacket.
The temperature change in the water is then accurately measured with a thermometer.
This reading, along with a bomb factor (which is dependent on the heat capacity of the
metal bomb parts), is used to calculate the energy given out by the sample burn.
After the temperature rise has been measured, the excess pressure in the bomb is
released.
Basically, a bomb calorimeter consists of a small cup to contain the sample, oxygen, a
stainless steel bomb, water, a stirrer, a thermometer, the dewar or insulating container (to
prevent heat flow from the calorimeter to the surroundings) and ignition circuit connected
to the bomb. By using stainless steel for the bomb, the reaction will occur with no volume
change observed.
Fuel value = Q = Mwx ∆TwxSHw