SK0014: PHYSICAL &

THERMOCHEMIST
INORGANIC CHEMISTRY
LECTURE 9:

RY
DR MOHD RAZALI SHAMSUDDIN
 Learning Outcomes:
By the end of this chapter, students should be able to:

01 Define thermochemistry, system and surrounding

02 Understand enthalpy and heat

Do calculations involving chemical reaction, enthalpy,

03 temperature, and heat capacity

04 Relates enthalpy and Hess’s Law

 Table of contents
Enthalpy and heat in
01 Thermochemistry, 02 chemical reaction
system and surrounding

Temperature
03 changes and heat
04 Hess’s Law
capacity

05 Enthalpy of reaction
 01
THERMOCHEMIST
RY, SYSTEM &
SURROUNDING
 ENERGY Thermal energy is
The ability to do work. Energy can be the energy of motion of
converted into work, heat, or radiation. In particles such as atoms,
simple words, energy is the capacity for doing molecules or ions.
work.

N
NUCLEAR
THERMODYNAMIC THERMOCHEMISTRY
VS
The study of energy the study
and its of chemical reactions and
transformations the energy changes
that involve heat

s t h e
d o e
h ere o?
W t g
hea
 Thermochemistry
surrounding
system
system
surrounding surrounding

system surrounding
system
system
surrounding

System: Surrounding:
the part that is being studied the rest that interacts with the system
 02
ENTHALPY AND
HEAT IN
CHEMICAL
REACTION
Heat (q) Is the energy transferred (heat flow) by a
system through temperature difference

Ice gets warmer while hand Cup gets cooler while hand
gets cooler gets warmer

Heat always flows from warmer to cooler objects

How do we
measure
heat?
 Heat VS Temperature
heat is energy, while temperature is a measure of energy
What happen to the temperature of the hand?
 Endothermic
absorb energy lower the temperature of their
from the surrounding area, creating a cooling
effect.
surrounding
system

surrounding
Ice cubes absorb heat energy from their
surroundings and melt to form liquid
water
(no chemical bonds are broken or
formed)
 Exothermic
energy is transferred into the
release energy to the surroundings.
surrounding
The change in enthalpy ( ΔH) will
be negative.

system

surrounding
 How do we
measure heat in
chemical
reactions?
Heat changes in chemical
reactions are most often
measured in the laboratory
under conditions in which the
reacting system is open to the
atmosphere. In that case, the
system is at constant pressure.
 ◆ Comes from the
Greek word:
“enthalpein”
◆ Meaning: to warm
◆ The exact value
cannot be
calculated, often
expressed as a
change in enthalpy,
∆H

The system at constant pressure

The experimental technique for measuring enthalpy changes is called
calorimetry. Calorimeter is a device for measuring quantities of heat.
The standard conditions for measuring enthalpies
are:
Temperature of 25oC (298 K)
Pressure of 1 atm (or 101 kPa)
Solutions having a concentration of 1.0 M

The bomb
calorimeter is
used to determine
the calorific values
of solid and liquid
fuels.
 Thermochemical equation
The quantity of energy released or absorbed as heat during a reaction is written and is represented
by H

two moles of hydrogen react with one mole of oxygen to make two moles of water,
the characteristic enthalpy change is -570 kJ

2H2(g) + O2 (g)  2H2O (l) ∆H = -570 kJ

exothermic
reaction of N2(g) with O2(g) to make NO(g), which has an enthalpy change of
181 kJ
N2(g) + O2 (g)  2NO (g) ∆H = +181 kJ
Don’t forget to balance the equation endothermic
 Enthalpy and stoichiometry

PCl3(g) + Cl2(g) → PCl5(g) ΔH = −88 kJ

What is the enthalpy change if 2 mol of PCl5 produced?
 Enthalpy and stoichiometry
PCl3(g) + Cl2(g) → PCl5(g) ΔH = −88 kJ
Revision:
What will happen to the equilibrium system if the temperature is
increased?
The reaction is exothermic, so:

PCl3(g) + Cl2(g) → PCl5(g) + temperature, T

If T is increased, the equilibrium would shift from right to left to

reduce T
 Exercise
A liquified petroleum gas tank in a home barbeque contains 13.2 kg of
propane, C3H8. Calculate the heat (in kJ) associated with the complete
combustion of all of the propane in the tank

C3H8(g) + 5O2(g)  3CO2(g) + 4H2O(g) ∆Hrxn = -2044 kJ

 Type of Enthalpy
The degree sign indicates standard Enthalpy of
Standard enthalpy states
formation, ∆Hf
change, ∆Ho Enthaply change when 1 mole of
Enthaply change for the the compound produced from its
reaction when all reactants constituent elements
and products are in standard
Eg: 2H2(g) + O2 (g) → 2H2O (l)
state
∆Hf = -570 kJ
Enthalpy of Enthalpy of
combustion, reaction, ∆Hrxn
∆Hc Enthaply change for a
Enthaply change for 1 mole of
a substance reacts with O2 chemical reaction
(combustion) Eg: PCl3(g) + Cl2(g) → PCl5(g)
Eg: N2(g) + O2(g) → 2NO(g) ΔHrxn = −88 kJ
ΔHc = 181 kJ

There are other types of enthalpy, depending on the reaction type

Standard Enthalpies
of Formation of
Some Inorganic
Substances at 25oc
 03
TEMPERATURE
CHANGES &
HEAT
CAPACITY
Heat capacity & Specific heat capacity

Heat Capacity, c: Specific Heat

the amount of heat (q) Capacity, C:
required to raise the The amount of heat (q)
temperature of a given required to raise the
quantity (m) of the substance temperature of one gram of
by one degree Celsius substance by one degree
Celsius.
q = c∆T q = mC∆T

Where ∆T = Tf - Ti
 Specific heat
capacity of
some common
materials
 Exercise
How much heat energy is needed to warm 250 g of water (about 1 cup)
from 22oC (about room temperature) to near its boiling point, 98oC? (The
specific heat of water is 4.18 J g-1 K-1)
 Exercise
If 25.0 g of Al cool from 310oC to 37oC, how many joules of heat energy are lost by
the Al? C = 0.897 J/g•K

How much heat energy is released when 7.1 g of substance is cooled from 100 oC to
room temperature (25 oC) ?
(The specific heat of the substance is 0.460 J g -1 oC-1)
 Thermal equilibrium
qsys = -qsurr
Or
-qsys = qsurr
-ve sign is written where the
exothermic reaction occurs (Tf
> Ti) Tfinal should be in between Tinitial of
both substance
 Supposed a block of metal initially at 55oC is
submerged into water initially at 75oC.
-ve sign at H2O
because it is
exothermic reaction
occurs
(Tf (H2O) > Ti (H2O) )
qmetal =-qwater qmetal = -qH2O

mmetal x Cmetal x ∆Tmetal = -mH2O x CH2O x ∆TH2O

Tfinal should be in between Tinitial

Ti (Al) 55oC < Tf (in between) < Ti (H2O) 75oC
of both substance
 Constant pressure calorimetry
Indirectly measure the heat change for the system

The calorimeter and its contents are

the surroundings and the reaction
occur is the system.

qsoln = -qrxn
qsoln = msoln x Csoln x ∆Tsoln = -qrxn Indirectly measured from
the solution’s information
*soln = solution
 Example
A 32.5 g aluminium initially at 45.8 oC is submerged into 105.3 g of water at 15.4oC. What is
the final temperature of both substances at thermal equilibrium? C Al= 0.903 J g-1 oC-1 CH2O =
4.18 J g-1 oC-1

A block of copper of unknown mass has an initial temperature of 64.5 oC. The copper is
immersed in a beaker containing 95.7 g of water at 22.7 oC. When the two substances reach
equilibrium, the final temperature is 24.2 oC. What is the mass of the copper block. [C Cu=
0.385 J g-1 oC-1 , CH2O = 4.18 J g-1 oC-1]
 Exercise
To determine whether a shiny gold-colored rock is actually gold, a chemistry student decides to measure
its heat capacity. She first weighs the rock and finds it has a mass of 4.7 g. she then finds that upon
absorption of 57.2 J of heat, the temperature of the rock rises from 25 oC to 57oC. Find the specific heat
capacity of the substance composing the rock and determine whether the value is consistent with the rock
being pure gold. [CAu= 0.129 J g-1 oC-1]

When 200.0 g of AgNO3 solution mixes with 150.0 g of NaI solution, AgI formed precipitates, and the
temperature of the solution rises by 1.34 oC. Assume the specific heat capacity of the solution is 4.184 J g -1
C , calculate heat of the reaction.
o -1
Relationship between ∆H and q

At constant pressure

∆Hrxn = qrxn (unit: kJ)

or
∆Hrxn = (unit: kJ mol-1)
 Example
250 cm3 of 0.50 mol dm-3 KOH solution at 31.0 oC is mixed with the same volume of 0.50 mol dm-3 HCl at
the same temperature in a polystyrene beaker. Given: ∆Horxn = -57.3 kJ mol -1, The specific heat capacity of
the solution is 4.184 J g-1 K-1
a) How much heat energy is released in this reaction?
b) Calculate the maximum temperature reached for the reaction.
 Exercise
a. The addition of hydrochloric acid to a silver nitrate solution precipitates silver chloride according to the reaction.

AgNO3(aq) + HCl(aq)  AgCl(s) + HNO3(aq)

When you combine 50.0 mL of 0.100 M AgNO3 with 50.0 mL of 0.100 MHCl in a coffee-cup calorimeter, the
temperature changes from 23.40 oC to 24.21oC. Calculate ∆Hrxn for the reaction as written. Use 1.0 g/mL as the
density of the solution and C = 4.18 J g -1 oC-1 as the specific heat capacity .

b. Zinc metal eggs with hydrochloric acid according to the balance equation:
Zn(s) + 2HCl(aq)  ZnCl(aq) + H2(g)
When 0.103 g of Zn(s) is combined with enough HCl to make 50.0 mL of solution in a coffee-cup calorimeter,
all of the Zn reacts, raising the temperature of the solution from. 22.5 oC to 23.7oC . Find ∆Hrxn for this reaction
is written. Use 1.0 g/mL as the density of the solution and C = 4.18 J g -1 oC-1 as the specific heat capacity.
 04
HESS’S
LAW
“The law states that the enthalpy change for a reaction that is carried out in a series of
steps is equal to the sum of the enthalpy changes for the individual steps”.
Consider the thermochemical cycle below:

∆H1 ∆H
A B A D

∆H3 ∆H2 ∆H1 ∆H3

∆H2
C D B C
∆H4

By Hess’s Law: What is the relationship between ∆H, ∆H1, ∆H2, and
∆H3?
∆H1 + ∆H2 = ∆H3 + ∆H4
∆H = ∆H1 + ∆H2+ ∆H3

39
Consider the following generic reaction.

A + 2B  C ∆H1

What is ∆H for reaction below?

a) 2A + 4B  2C ∆H2 = ?
b) C  A + 2B ∆H3 = ?

a) By comparing the equation,

equation a = 2 (A + 2B  C)
thus, ∆H2 = 2(∆H1 )
b) By comparing the equation,
equation b = - (A + 2B  C) -ve means reversed equation
thus, ∆H3 = -∆H1
Consider the following generic reaction.

A + 2B  C ∆H1
C  2D ∆H2
What is ∆H for reaction:
A + 2B  2D

A + 2B  C ∆H1
C  2D ∆H2
Overall: A + 2B  2D ∆H = ∆H1 + ∆H2
 C(s) + 2H2(g) →CH4(g) ∆Hof = ??
CH4(g) + 2O2(g) →CO2(g) + 2H2O(l) ∆Hoc [CH4]= -891 kJmol-1
C(s) + O2(g) → CO2(g) ∆Hof [CO2]= -393 kJmol-1
H2(g) + ½O2(g) → H2O(l) ∆Hof [H2O]= -286 kJmol-1
Given the following data:
SrO(s) + CO2(g) → SrCO3(s) ΔH = −234 kJ
2SrO(s) → 2Sr(s) + O2(g) ΔH = +1184 kJ
2SrCO3(s) → 2Sr(s) + 2C(s) + 3O2(g) ΔH = +2440 kJ
Find the ΔH of the following reaction:
C(s) + O2(g) → CO2(g)
 05
ENTHALPY
OF
REACTION
 ENTHALPY OF REACTION
The enthalpy of reaction for a chemical reaction is the difference
between total product and total reactant molar enthalpies, calculated
for substances in their standard states.

∆Horxn = Sum of ∆Hof of the products – sum of ∆Hof of the reactants

Let say,
aA + bB → cC + dD

∆Horxn = ∑∆Hof (products) – ∑∆Hof (reactants)

= [c(∆Hof C) + d(∆Hof D) ] – [a(∆Hof A) + b(∆Hof B)]
 Example
The standard enthalpies of formation for carbon dioxide, ethane and water are -393, -85,
and -286 kJmol-1, respectively. Calculate the enthalpy change for the reaction.

C2H6 (g) + O2 (g) → 2CO2 (g) + 3H2O (l)

Exercise Exercise
a. Calculate ΔH for this reaction:
CH4(g) + NH3(g) ---> HCN(g) + 3H2(g)

given:
N2(g) + 3H2(g) ---> 2NH3(g) ΔH = −91.8 kJ
C(s) + 2H2(g) ---> CH4(g) ΔH = −74.9 kJ
H2(g) + 2C(s) + N2(g) ---> 2HCN(g) ΔH = +270.3 kJ

b. Calculate the standard enthalpy of reaction for the combustion of methane:

CH4(g)+2O2(g)→CO2(g)+2H2O(g) ΔHrxn=?

ΔHof [CH4(g)] =−75 kJ/mol

ΔHof [O2(g)] = 0 kJ/mol
ΔHof [CO2(g)] =−394 kJ/mol
ΔHof [H2O(g)] =−284 kJ/mol
THANK YOU