1.

3 Calorimetry
1.3.1 Heat capacity and specific heat
 Specific heat capacity (s) – the amount of heat required to raised the temperature of 1 gram of substance by 1 degree
Celsius or Kelvin. Unit → J˚C-1g-1 or JK-1g-1.
 Heat capacity (C) – amount of heat needed to raise the temperature of a given quantity of the substance by 1 degree
Celsius or Kelvin. Unit J ˚C-1 or JK-1.
 The relationship between the heat capacity and specific heat of a substances is
C=m×s
 Heat capacity of substance = mass of substance (m) × specific heat of substance (s)

Heat Capacity (C)

Amount of heat needed to

raise temperature of a given
An extensive property. Unit JoC-1 or JK-1
quantity of substance by 1 oC
or K
 Heat capacity (C)
• The change in temperature (∆T) of a system is proportional to quantity heat supplied, q.
q
T =
C
• The system with a large heat capacity undergoes only small increase in temperature for a given input of heat.

1
T =
C
 Heat capacity at constant volume, Cv (J K-1) – Isochoric Process
 U 
C v=  
 T  v
 Molar heat capacity at constant volume, Cv,m (J K-1mol-1) – the heat capacity per mole of material.
 If the heat capacity is independent of temperature over the range temperatures of interest, then a measurable
change of temperature ∆T brings about a measurable increase in internal energy ∆U.
U
Cv =
T
 ∆U = Cv∆T and ∆U = qv
 qv = Cv∆T

2
 Heat capacity (C)
• For liquids and solids, ∆H and ∆U are very close to one another.
• Consequently, Cp and Cv are essentially the same for solids and liquids.
• For gases, however, the ∆(PV) term is appreciable, and there is significant difference between Cp and Cv
.
• For ideal gas
PV = nRT
• The relationship between Cp and Cv for gases can be derived as follows.

H = U + PV
H = U + (nRT)
H U T(nR)
= +
T T T
CP = Cv + nR 3
 Heat capacity (C)
 Heat capacity at constant pressure, Cp (J K-1) – Isobaric Process

 H 
C P=  
 T  p
 Molar heat capacity at constant pressure, Cp,m (J K-1mol-1) – the heat capacity per mole of
material.
 If the heat capacity is independent of temperature over the range temperatures of interest, then
a measurable change of temperature ∆T brings about a measurable increase in enthalpy, ∆H.

 ∆H = Cp∆T and ∆H = qP H
CP =
 qP = CP∆T T

4
 Specific heat capacity (s)
 The amount of heat releases or absorbed

q = m × s × ∆T

 Where m is the mass of the sample and ∆T is the change in temperature.

 If the heat capacity is given per mole of the substance, it is called the molar heat capacity and the unit
is J˚C mol-1 or JK-1mol-1.

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 Calculation:
qreaction = - (qcalorimeter + qsolution)
- [(Ccal × ∆T) + (msol × ssol × ∆T)]
qcalorimeter = heat absorbed/released by calorimeter
= Ccal × ∆T
C is the heat capacity of calorimeter
∆T is the temperature change of the solution in the calorimeter

qsolution = heat absorbed/released by the solution to raise/decrease its temperature

= msol × ssol × ∆T

msol = mass of solution in the calorimeter

ssol = specific heat of the solution
∆T = the temperature change of the solution in the calorimeter.
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Device used – calorimeter

1. Constant pressure calorimetry

: Use coffee cup calorimeter

Heat change in system = enthalpy change

qp = ∆H

Simple calorimeter
(Coffee cup calorimeter)
not for combustion
Simple calorimeter
 Calorimetry
If the process is carried out under constant pressure (eg: reaction in a
coffee cup calorimeter) and the only work allowed is pressure-volume
work, then heat measured is equal to enthalpy change.

∆H = ∆U + ∆(PV) ∆H = ∆U + P∆V

∆H = ∆U + P∆V since , ∆U = w + q
∆H = w + q + P∆V and w = -P∆V
∆H = -P∆V + q + P∆V
∆H = -P∆V + q + P∆V
∆H = qp 8
2. Constant volume calorimetry
: Use adiabatic bomb calorimeter

Heat change in system = internal energy change

qv = ∆U

Amount of heat released:

q = mc∆t Or q = c∆t

Q reaction = (qcalorimeter + qsolution )

= ( c∆t + mc∆t)
 Calorimetry
If the process is carried out under constant volume (e.g: reaction in
a bomb calorimeter), then heat measure is equal to the change in
internal energy

∆U = w +q
w = - P∆V
For constant volume process, ∆V = 0 , therefore, w =
0
∆U = qv
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 DETERMINING HEAT OF REACTION
50 mL of 0.5M NaOH in a coffee-cup calorimeter at 25 oC is added to 25 mL of 0.5M HCl at 25 oC.
After stirring, the final temperature is 27.21 oC. Calculate qsolution (in J) and ∆Hrxn (in kJ/mol)
(Density of solution: 1 g/mL and specific heat capacity of water = 4.184 J/g.K)
Answer:
Heat of reaction = m x s x ∆T
q = (25 + 50) X 4.18 X (27.21 – 25)
= 692.84 J
= 0.69 kJ
nH+ = 0.5 M x 0.250 L = 0.0125 mol
nOH- = 0.5 x 0.050 L = 0.025 mol
H+ is limiting reactant.
∆H = q/n =- 0.69/0.0125 =- 55.4 kJ mol-1
 DETERMINING HEAT OF COMBUSTION
1.435g of napthalene, C10H8, was burned in a bomb calorimeter. The temperature of water rose from 20.28 oC
to 25.95 oC. If heat capacity of the bomb plus water was 10.17 kJoC-1, calculate ∆Hc of naphthalene.
m = 1.435g Mr = 128
C = 10.17 kJoC-1
∆t = 25.95-20.28 = 5.67 °C

q = C∆t
= 10.17 kJoC-1 x 5.67 oC
= 57.66 kJ
n of C10H8 = m/Mr = 1.435g/ 128gmol-1
= 0.011 mol
∆Hc = q/n
= 57.66kJ/0.011mol
= - 5241.8 kJmol-1
When C2H5OH is burnt using the simple calorimeter, the following results are obtained:
Mass of C2H5OH before combustion: 400.0g
Mass of C2H5OH after combustion: 398.5g
Calculate ∆Hc of C2H5OH
Mass of water in the metal calorimeter: 500g
Increase in temperature : 12.95 OC
Specific heat capacity of water: 4.18 J g-1K-1

q = mc∆t
= 500 X 4.18 X 12.95
= 27,066 J = 27.07 kJ

Mass of ethanol = 400-398.5 = 1.5g

n of C2H5OH burnt = mass/molar mass
= 1.5g/46 gmol-1
= 0.0325 mol
∆Hc =q/n=27.07 kJ/ 0.0325 mol = -830 kJmol-1
1.4 Hess’s Law
1.4.1 Definition and calculation
• States that when reactants are converted to products, the change in enthalpy is the same whether
the reaction takes place in one step or in a series of steps
• Important when ∆H difficult to carry out directly in a calorimeter

Route 1
A+B C+D
∆H1

∆H3
∆H2
E ∆H1= ∆H2+ ∆H3
Route 2

Hess law states that the total enthalpy change accompanying a chemical reaction is independent
of the route by which the chemical reaction takes place.
• Rules in Hess’s Law:
• The total amount of energy released or absorbed is directly proportional to the number of
moles of the reactants used.
• The ∆H for the reverse reactions is equal in magnitude but opposite in sign to the enthalpy
change for the forward reaction.

Steps involved in solving enthalpy of combustion problems

1. Balance the individual equations.
2. If necessary look up standard enthalpies.
3. Flip equations around if necessary to cancel out terms on opposite sides.
4. Changing the equation around requires a sign change of the H of that individual
step.
5. Sum up the individual steps.
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 Example
Calculate the standard enthalpy of combustion of the transition of
C(s, graphite) → C(s, diamond), given;
C(s, graphite) + O2 → CO2 ∆Ho = -393.5 kJ/mol
CO2 → C(s, diamond) + O2 ∆Ho = + 395.41 kJ/mol
1) equations are balanced
2) no need to flip an equation around because it is possible to cancel out a couple terms as is.
3) canceling out the O2 and the CO2 species
4) writing the overall reaction

Summing the two enthalpies together.

∆H= -393.5 kJ/mol + 395.41 kJ/mol
∆H = +1.91 kJ/mol. 16
 Calculating the Enthalpy Changes
METHODS ON CALCULATING THE ENTHALPY CHANGES
A. Using Formula (direct method)

∆H0 = Sum∆H0f (products) - Sum∆H0 f(reactants)

B. Algebraic method (indirect method)
- using thermochemical equation
- Hess’s Law
C. Energy Cycle method (indirect method)
- using thermochemical equation
- Hess’s Law

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 FORMULA METHOD
(Direct method)
aA + bB cC + dD
H◦rxn = S nH◦f (products) - S mHf◦ (reactants)
Hrxn
◦
= [ cH◦f (C) + dH◦f (D) ] - [ aH◦f (A) + bH◦f (B) ]

The standard enthalpy of formation of any element in its most stable form is ZERO

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Benzene (C6H6) burns in air to produce carbon dioxide and liquid water. How much heat
is released per mole of benzene combusted? The standard enthalpy of formation of
benzene is 49.04 kJ/mol.
2C6H6 (l) + 15O2 (g) 12CO2 (g) + 6H2O (l)

H0rxn = S nH0f (products) - S mHf0 (reactants)

H0rxn = [ 12H0f (CO2) + 6H0f (H2O)] - [ 2H0f (C6H6)]

H0rxn = [12(–393.5) + 6(–187.6)] – [2(49.04)] = -5946kJ

-5946 kJ
= - 2973 kJ/mol C6H6
2 mol

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 ALGEBRAIC METHOD
(Indirect method)
Using thermochemical equations.

RULES IN USING THERMOCHEMICAL EQUATION

1. The stoichiometric coefficients always refer to the number of moles of a
substance
2. If you reverse a reaction, the sign of DH changes
3. If you multiply both sides of the equation by a factor n, then DH must change
by the same factor n.
4. The physical states of all reactants and products must be specified in
thermochemical equations.

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 RULES IN USING
THERMOCHEMICAL EQUATION
1. The stoichiometric coefficients always refer to the number of
moles of a substance
H2O (s) H2O (l) H = 6.01 kJ/mol

2. If you reverse a reaction, the sign of H changes

H2O (l) H2O (s) H = -6.01 kJ/mol

3. If you multiply both sides of the equation by a factor n, then

H must change by the same factor n.

2H2O (s) 2H2O (l) H = 2(6.01) = 12.02 kJ

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 RULES IN USING
THERMOCHEMICAL EQUATION
4. The physical states of all reactants and products must be specified
in thermochemical equations.
H2O (s) H2O (l) H = 6.01 kJ/mol

H2O (l) H2O (g) H = 44.0 kJ/mol

How much heat is evolved when 266 g of white phosphorus (P4) burn
in air?
P4 (s) + 5O2 (g) P4O10 (s) H = -3013 kJ/mol
1 mol P4 -3013 kJ
266 g P4 x x = -6470 kJ
123.9 g P4 1 mol P4

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Calculate the standard enthalpy of formation of CS2 (l) given that:
C(graphite) + O2 (g) CO2 (g) H0rxn = -393.5 kJ/mol
S(rhombic) + O2 (g) SO2 (g) H0rxn = -296.1 kJ/mol
CS2(l) + 3O2 (g) CO2 (g) + 2SO2 (g) Hrxn
0 = -1072 kJ/mol

1. Write the enthalpy of formation reaction for CS2

C(graphite) + 2S(rhombic) CS2 (l)

2. Add the given rxns so that the result is the desired rxn.
C(graphite) + O2 (g) CO2 (g) H0rxn = -393.5 kJ/mol
2S(rhombic) + 2O2 (g) 2SO2 (g) H0rxn = -296.1 kJ/mol x 2
CO2(g) + 2SO2 (g) CS2 (l) + 3O2 (g) H0rxn = +1072 kJ/mol
C(graphite) + 2S(rhombic) CS2 (l)
H0rxn = -393.5 + 2(-296.1) + 1072 = 86.3 kJ/mol 23
 ALGEBRAIC METHOD
(HESS’s LAW)
• the heat evolved or
absorbed in a chemical
process is the same
whether the process takes
place in one or in several
steps.
ALGEBRAIC METHOD
(HESS’s LAW)
• ∆H1 shows the magnitude of
the single step reaction.
• ∆H2 and ∆H3 when combined
are equivalent to ∆H1,
demonstrating Hess’s Law.