CHM271

CHAPTER 1
THERMOCHEMISTRY
Rosmawati Abdul Aziz
rosmawatiaa@uitm.edu.my
 CHAPTER 1 : THERMOCHEMMISTRY
1.1 Exothermic and endothermic reactions
1.2 Enthalpy change
1.2.1 Enthalpy of formation
1.2.2 Enthalpy of combustion
1.2.3 Enthalpy of neutralization
1.3 Determination of enthalpy change of reaction
1.3.1 Using standard enthalpy of formation
1.3.2 Calorimetry (Simple calorimeter and bomb calorimeter)
1.3.3 Hess’s Law and calculations
 INTRODUCTION

THERMOCHEMISTRY
Study of energy changes during chemical reactions or changes of state.
▪ Energy changes involves exothermic & endothermic reactions
 EXOTHERMIC REACTION
DEFINITION Process that release energy from the system to
surroundings in form of heat / thermal.
▪ Enthalpy of the reaction system decreases
▪ The products have lower energy than the reactants
▪ Increase the temperature of surroundings ;
causing the reaction mixture and its surroundings
to become hotter.
▪ Negative value of ΔH.
▪ feel hot because it is giving heat to you.
▪ eg; combustion & forming a chemical bond
 ENDOTHERMIC REACTION
DEFINITION Process that absorbs energy from the surroundings to
system in form of heat / thermal.
▪ Enthalpy of the reaction system increases
▪ The products have higher energy than the reactants
▪ Decreases the temperature of surroundings ; causing
the reaction mixture and its surroundings to become
colder.
▪ Positive value of ΔH.
▪ feel cold because it is taking heat away from you.
▪ eg; electrolysis & breaking a chemical bond
 ENTHALPY, H
DEFINITION total heat content of a substance at constant pressure.
▪ total enthalpy, H, of a system cannot be measured directly.
Thus, change in enthalpy, ΔH, is a more useful quantity than its
absolute value.
▪ Sign of enthalpy change (∆H)
▪ ∆H >0 (positive) → Endothermic
▪ ∆H <0 (negative) → Exothermic
▪ Heat of Reaction = amount of heat absorbed or released when the
reaction occurs at constant pressure.
▪ Focusses on :
1. Enthalpy of formation
2. Enthalpy of combustion
3. Enthalpy of neutralization
 ENTHALPY OF FORMATION, ∆H°f
DEFINITION
Enthalpy change which occurs when one mole of the compound is
formed from its elements under standard conditions, and with everything
in its standard state.
▪ standard ∆H°f for an element in its standard state is zero.
▪ Absorbs/releases no energy to form a compound that occurs naturally.
▪ standard state : pure substances in a specificied state
▪ Example: Solid Liquid Gas
Carbon, C (graphite) Bromine Br2 (l) Hydrogen, H2 (g)
Aluminium, Al (s) Mercury H2 (l) Oxygen,O2 (g)
Lithium, Li (s) Nitrogen,N2 (g)
Magnesium, Mg (s) Chlorine, Cl2 (g)
Silver, Ag (s) Flourine, F2 (g)
 ENTHALPY OF FORMATION, ∆H°f

FORMATION REACTION
▪ There is never a compound on the reactant side, only element.

WRONG 6 CO2 + 6 H2O → C6H12O6 + 6O2

CORRECT 6 C (graphite) + 6 H2 (g) + 3 O2 (g) → C6H12O6
▪ a formation reaction involves making a substance from its elements and
ONLY the elements.
▪ must end up with 1 mole of the compound

DETERMINATION OF ΔH°sys
▪ Can be exothermic or endothermic reaction
ΔH°sys = ΔH°f (product) - ΔH°f (reactant)
 DETERMINATION OF ΔH°:
FROM ENTHALPY CHANGES OF FORMATION
EXAMPLE
Determine the enthalpy change for the reaction between C2H4 and HCl
gases to make C2H5Cl from the standard enthalpy of formation values in
the table.

Substances ΔH°f (kJ mol-1) SOLUTION

C2H4(g) +52.2
HCl(g) -92.3
ΔH° = ΔH°f (product) - ΔH°f (reactant)
C2H5Cl(g) -109 = -109 - [52.2+(- 92.3)] kJ mol-1
= -109 – [- 40.1] kJ mol-1
= - 68.9 kJ mol-1
 PRACTICE
Determine the enthalpy change in the following reaction:

Substances ΔH°f (kJ mol-1)

Li2CO3 (s) -1216
Li2O (s) -596
CO2 (g) -394
Ans: +226 kJ mol-1
 ENTHALPY OF COMBUSTION, ∆H°c
DEFINITION
Enthalpy change which occurs when one mole of the compound is
burned completely in oxygen under standard conditions, and with
everything in its standard state.

▪ Always exothermic reaction

▪ shown by the negative sign.

C (graphite) + O2(g)→ CO2 (g) ∆H = -394 kJ mol-1

shows that 394 kJ of heat energy are released when equation quantities
of carbon and oxygen combine to give carbon dioxide.
 ENTHALPY OF NEUTRALIZATION, ∆H°N
DEFINITION
Enthalpy change which occurs when an acid and a base react to form
one mole water and a salt under standard conditions.

▪ Always measured per mole of water formed.

▪ Always negative sign.

NaOH (aq) + HCl (aq) → H2O (g)→ NaCl (aq) ∆H = - 57.9 kJ mol-1

shows that 57.9 kJ of heat energy are released when NaOH and HCl
react to form one mole of water.
 DETERMINATION OF ΔH°:
CALORIMETRY
SPECIFIC HEAT (s)
C = ms
▪ Amount of heat required to raise the
temperature of one (1) gram of the C = Heat Capacity (J/K or J/°C)
m = mass (g)
substance by one (1) degree Celsius s = Specific Heat (J/g K or J/g °C)
or Kelvin.
▪ Unit = J/g K or J/g °C
▪ Specific heat of water = 4.2 J g-1°C-1 q = msΔT @ q = CΔT
q = Heat (J)
HEAT CAPACITY (C)
s = Specific Heat (J/g K or J/g °C)
▪ Amount of heat required to raise the C = Heat Capacity (J/K or J/°C)
temperature of a given quantity of the ΔT = Temperature Changes (K or °C )
substance by one (1) degree Celsius = Tfinal - Tinitial
or Kelvin.
▪ Unit = J/K or J/°C
EXAMPLE
Calculate the amount of heat necessary to raise the temperature of 12.0 g
of water from 15.4°C to 93.0°C. The specific heat of water = 4.18 J/g °C

SOLUTION
ΔT = (93.0 - 15.4) °C = 77.6 °C

qH2O = msΔT
= 12.0g × 4.18 J/g·°C × 77.6 °C
= 3892.42 J

PRACTICE
Determine the heat required to raise the temperature of 2,500 g of water
from 27°C to 72°C. Given the specific heat of water is 4.184 J/g °C.

Ans : 470250 J
 CALORIMETRY

▪ Calorimeter
▪ devise used to measure the enthalpy change in chemical reactions.
▪ Function : Avoid the heat flow to or from surroundings.
▪ Available in two (2) types
1. constant pressure – coffee cup calorimeter
2. constant volume – bomb calorimeter

qreaction = - (qsol + qcal)

qreaction = Heat of reaction (J)

qsol = Heat of solution (J)
qcal = Heat of calorimeter (J)
 CALORIMETER
1. Coffee cup calorimeter (constant pressure calorimetry)

▪ used to measure heat change for noncombustion reactions.

▪ Can be sophisticated and expensive or simple and cheap
▪ Styrofoam cup is used as a calorimeter, because it is a container
with good insulated walls to prevent heat exchange with the
environment.
qreaction = - qsol
2. Bomb calorimeter (constant volume calorimetry)

▪ More accurate method of finding enthalpy of combustion.

▪ Heat loss to the surrounding is reduced to zero.

qreaction = - (qsol + qcal)

DETERMINATION OF ΔH°: CALORIMETRY

SITUATION 1 value of heat capacity of calorimeter NOT GIVEN

▪ Assume calorimeter is totally insulated which it do not

absorb/release heat from the reaction.
▪ Ccal = 0

qreaction = - (qsol + qcal) ; Ccal = 0

qreaction = - (qsol + 0)
qreaction = - qsol
EXAMPLE
A lead pallet having a mass of 26.47g at 89.98°C was placed in a
calorimeter containing 100 mL of water. The water temperature rose from
22.5°C to 23.17°C. Determine the enthalpy change for the reaction. Given
specific heat of water = 4.18 J/g °C, density of water = 1g/mL and molar
mass of Pb = 207 g/mol.

SOLUTION
EXAMPLE
Complete combustion of 1.85 g of butanol, C4H9OH in a calorimeter raised
the temperature of 200 cm3 of water by 8.1 °C. Determine the enthalpy of
combustion of butanol. Given specific heat of water = 4.2 Jg-1K-1 ;density of
water =1.0 gcm-3; relative atomic weight: H=1, C=12, 0=16)

SOLUTION
DETERMINATION OF ΔH°: CALORIMETRY

SITUATION 2 value of heat capacity of calorimeter GIVEN

▪ Meaning that calorimeter will be able to absorb/release the heat

from reaction.
▪ Therefore, heat release by reaction(combustion) will be absorb
by water(solution) and calorimeter.
▪ Heat evolved in a bomb calorimeter combustion reaction (qreaction)
is absorbed by the steel bomb (qcal) and the water in the water
bath (qwater).

qreaction = - (qsol + qcal)

EXAMPLE
A 0.444 g sample of sucrose (C12H22O11) is burned in a bomb calorimeter
and the temperature increases from 20.00 °C to 22.06 °C. The
calorimeter contains 748 g of water, and the bomb has a heat capacity of
420 J/°C. Calculate ΔH for the combustion reaction. Given specific heat
of water = 4.2 Jg-1K-1 ; relative atomic weight: H=1, C=12, 0=16)

SOLUTION
EXAMPLE
A 0.444 g sample of sucrose (C12H22O11) is burned in a bomb calorimeter
and the temperature increases from 20.00 °C to 22.06 °C. The
calorimeter contains 748 g of water, and the bomb has a heat capacity of
420 J/°C. Calculate ΔH for the combustion reaction. Given specific heat
of water = 4.2 Jg-1K-1 ; relative atomic weight: H=1, C=12, 0=16)

SOLUTION
 DETERMINATION OF ΔH°: HESS’S LAW
DEFINITION
The overall enthalpy change for a reaction is equal to the sum of the
enthalpy changes for the individual step in the reaction.

▪ Published by Germain Hess in 1840

▪ 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.
▪ Very useful to calculate ∆H that cannot be determined directly.
DETERMINATION OF ΔH°: HESS’S LAW

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
EXAMPLE
Determine the standard enthalpy of combustion of the transition of :
C(s, graphite) → C(s, diamond),
Given:
C(s, graphite) + O2 → CO2 ΔHo = -393.5 kJ/mol
CO2 → C(s, diamond) + O2 ΔHo = + 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
SOLUTION
EXAMPLE
Calculate the enthalpy formation of methane CH4;

CH4(g) + H2O(l) → CO(g) + 3H2(g)

CO(g) + H2(g) → C(gra) + H2O(g) ΔH° = -131.3 kJ

C(gra) + 2H2(g) → CH4(g) ΔH° = -74.8 kJ

SOLUTION
Question 1 PRACTICE
Differentiate between exothermic & endothermic reaction in terms of
definition, temperature and energy diagram.

Question 2
Give a definition of the following;
a) Enthalpy change
b) Enthalpy of combustion
c) Enthalpy of formation
Question 3
Reaction between methane and chlorine is:
CH4(g) + 2Cl2(g) → CCl4(l) + 2H2(g)

And given ; ΔHf˚ CCl4 (l) = –128.4 kJ/mol and ΔHf˚ CH4(g) = -75kJ/mol

Calculate the enthalpy change for the reaction. Ans: - 53.4 kJ

Question 4
PRACTICE
A 1 g sample of octane (C8H18) is burned in a bomb calorimeter containing
1200 grams of water at an initial temperature of 25.00ºC. After the reaction,
the final temperature of the water is 33.20ºC. The heat capacity of the
calorimeter is 837 J/ºC. The specific heat of water is 4.184 J/g ºC.
Determine the heat of combustion of octane in kJ/mol.

Question 5
Given the following ΔH° values,

H2(g) + ½O2(g) → H2O(l) = -285.8 kJ

H2O2(l) → H2(g) + O2(g) = 187.6 kJ

Calculate the standard enthalpy of formation for the reaction

H2O2(l) → H2O(l) + ½O2(g),
 PRACTICE
Question 6
Determine the standard enthalpy change, ΔHo, for the formation of
1 mol of strontium carbonate (the material that gives the red color in
fireworks) from its elements.

Ans: -1220 kJ
 PRACTICE
Question 7

2C (s) + 2H2O → CH4(g) + CO2 (g)

Determine the standard enthalpy change, ΔHo, for this reaction from
the following standard enthalpies of reaction :

Ans: 15.3 kJ
 “Knowledge is power,
community is strength &
attitude is everything”

“Knowledge Shared
= Knowledge2 ”

32