TRT 401 PHYSICAL

CHEMISTRY
PART 1: FIRST LAW
THERMODYNAMIC

Basic concept:
1. Work, heat and energy
2. The internal energy
3. Expansion work
4. Heat transaction
5. Adiabatic changes

Thermochemistry:
1. Standard enthalpy
changes
2. Standard enthalpies of
formation
3. The temperature
dependence of reaction
enthalpies.

First Law
Thermodyna
mic
State of function and exact differentials:
1. Exact and inexact differentials
2. Changes in internal energy
3. The Joule Thomson effect

Work
Work (w) is defined as the force (F) that produces the
movement of an object through a distance (d):
Work = force distance
w=Fxd
Work also has units of J, kJ, cal, kcal, Cal, etc.
The two most important types of chemical work are:
the electrical work done by moving charged particles.
the expansion work done as a result of a volume
change in a system,
particularly from an expanding or
contracting gas. This is also known
as pressure-volume
work, or PV work.
PV work occurs when the force is the result of a volume
change against an
external pressure.

The example of PV work in the cylinder of an automobile engine

The combustion of the gasoline causes gases within the cylinder to
expand, pushing the piston outward and ultimately moving the
wheel of the car.
The relationship between a volume change (V) and work (w):
W= -P V
Where P is external pressure
The units of PV work are Latm; 1 Latm = 101.3 J.
If the gas expands, V is positive, and the work term
will have a negative sign (work energy is leaving the
system).
If the gas contracts, V is negative, and the work term
will have a positive sign (work energy is entering the
system).
If there is no change in volume, V = 0, and there is
no work done. (This occurs in reactions in which
there is no change in the number of moles of gas.)

Expansion Work

If the gas expands, V is positive, and the work term will

have a negative sign (work energy is leaving the system).
If the gas contracts, V is negative, and the work term will
have a positive sign (work energy is entering the system).
If there is no change in volume, V = 0, and there is no work
done. (This occurs in reactions in which there is no change in the

e expansion is expansion against zero opposing force.

W=0
ork is done when a system expand freely. Expansion of this kind occurs when a
ds into a vacuum.
c) Expansion against constant pressure now suppose that the
external pressure is
constant throughout expansion.

Therefore, if we write the change

in volume as V=Vf -Vi

d) Reversible Expansion
A reverse change in thermodynamic is a change that can be
reversed by an infinitesimal modification of a variable.
The key infinitesimal sharpen the everyday meaning of the word
reversible as something that can change direction.

d) Isothermal reversible expansion

When the volume is greater than the initial volume, as in

expansion, the logarithm
in above equation is positive and hence
w<0. In this case the system has done work
on the surroundings
and there is a corresponding reduction in its internal energy.
From the equation also show that more work is done for a given
change of volume when temperature is increased:
at higher temperature the greater pressure of the confined
gas needs a higher
opposing pressure to ensure
reversibility and the work done is
correspondingly greater.

Table 1
Type of work

Type of work
Variables

Conventional
unit

Volume expansion

Pressure (P), volume (V)

Pa m3 = J

Stretching

Tension (), length (l)

N m= J

Surface expansion

Surface tension (), area ()

(Nm-1)(m2) = J

Electrical

Electrical potential(),
Electrical change (q)

VC=J

Example 1:
Inflating balloon requires the inflator to do pressure-work on the
surroundings. If balloons is inflated from a volume of 0.100L to 1.85L
against an external pressure of 1.00 atm, how much work is done (in
joules)?

Sort: you are given the initial and

final volumes of the volumes of
the balloon and the pressure
against which its expands. The
balloon and its contents are the
system

Given: V1 = 0.100L, V2 = 1.85L,

P=1.00 atm
Find: W

Strategy: the equation W= -P V

specifies
the amount of work done during a
volume
Change against an external
pressure.

Conceptual Plan:
P,V W

Solve: To solve the problem,

compute the value of V and
substitute it, together with
P, into the equation.

W= -P V

Solution:
V = V1 - V2
= 1.85L - 0.100L
= 1.75L
W= -P V
= - 1.00 atm x 1.75L
= -1.75L.atm
The units (J) are correct for work. The sign-1.75
it should
an Jexpansion:
work
L.atmbe
x for
101.3
= -177 J
surroundings
expanding
The units ofby
thethe
answer
(L.atm) balloon.
1L.atm
can be converted to joules using
101.3J = 1L.atm

Example 2:
A sample of argon of mass 6.56 g occupies 18.5
dm3 at 305K.
(a)Calculate the work done when the gas
expands isothermally against a constant
external pressure of 7.7 kPa until its volume
has increased by 2.5 dm3.
(b) Calculate the work that would be done if the
same expansion occurred reversibly.

(a)

(b
)

HEAT
Heat is a exchange of thermal energy between a system and its
surroundings caused
by temperature difference.

Notice the distinction between heat and temperature. Temperature

is a measure of
the thermal energy of a sample matter. Heat is
transfer of the thermal energy.
erature Change and Heat Capacity when system absorbs heat (q) its temperatu
ges by T:
Heat (q)

System
T

Experimental measurements demonstrate that the heat absorbed by a

system and its
corresponding temperature change are directly proportional : q T.
The constant of
proportionality between q and T is called the heat capacity.

Heat Capacity

Heat capacity (C) is the amount of heat (q) a substance

must absorb to raise its temperature(T) by 1 C.
- Heat capacity has units of J/C (or J/K), and is an
extensive property,
depending on the sample size.

Two type of heat capacity:

1) Heat capacity at constant volume:

2) Heat capacity at pressure constant

Specific Heat
The specific heat (c, or specific heat capacity, C s) of an
object, is the quantity of heat required to change the
temperature of 1 gram of a
substance by 1 C (or K):

- Specific heat has units of J / g C, and is an intensive

property, which is independent of the sample size.
The molar heat capacity (Cm), is the quantity of heat
required to change
the temperature of 1 mole of a
substance by 1 C (or K):

Heat Transactions

In general the change in internal energy of a system:

dwe is work in addition(e for extra) to the expansion work

wexp = 0, when a system kept a constant volume cannot do any expansion work.

he system also incapable of doing any other kind of work (if it is not, for instanc
electrochemical cell connected to an electric motor), then dw e = 0 too. Under th
cumstances :
Heat transfer at volume
We express this relationship by writing, dU=dqv where the subscript
implies a change at constant volume. For measurement change,

A bomb Calorimeter
The amount of heat absorbed by the
water in the calorimeter is equal to
the energy that is released by the
reaction (but opposite in sign).

qcal : heat absorbed by the entire

calorimeter assembly
Ccal: heat capacity of entire calorimeter
assembly
If no heat escape from the

container:

During
the
summer,
you
have
experienced the effect of waters high
specific
heat capacity.
Example:
Sacramento (an inland city) and San
Francisco
(a coastal city) can be
18oC (30oF).
San Francisco enjoy cool 20oC (68oF)
while Sacramento bakes at nearly 38oC
Why the
large temperature difference?
(100oF).
San
Francisco
sit
on
peninsula,
surrounded by the Pacific Ocean. Water
absorbed much the suns heat without
undergoing
a
large
increase
in
temperature.
While the Sacramento, with its low heat
capacity undergoes a large increase in
temperature as it absorbs a similar
amount of heat.
heat = mass x specific heat x temperature

e high heat capacity of water surrounding

n Francisco results in relatively cool summer
mperatures.

q= m x Cs x T

specific heat can be used to quantify the relationship between the amount of hea
ed to a given amount of the substance and the corresponding temperature increa

equation is:

heat = mass x specific heat x temperature

q= m x Cs x T

Example 2:
Suppose you find a copper penny (minted
pre-1982 when pennies were almost
entirely were almost entirely copper) in the
snow. How much heat is absorbed, by the
penny as it warms, from the sun
temperature of the snow, which is -8.0oC,
to the temperature of your body, 37oC?
Assume the penny is pure copper and has
a mass of 3.10g.

Sort: You are given the mass of

copper as well as its initial and
final temperature. You are asked
to find the heat required for the
given temperature change

Given:
m = 3.10 g copper
Ti = -8.0 oC
Tf = 37.0 oC
Find : q

Strategy: The equation q = m

Conceptual Plan:
x Cs x T give the relationship
Cs , m, T q
between the amount of heat (q)
q = m x Cs x T
and the temperature change (T
Relationship Used:
)
q = m x Cs x T
Cs = 0.385 J/g.oC
Solve: Gather the necessary
quantities for the equation in
the correct units and
Substitute these into the
equation to compute q.

Solution:
T = Tf Ti
= 37.0oC (-8.0oC) = 45.0oC
q = m x Cs x T
= 3.10 g x 0.385 J
x
45.0oC = 53.7J
g. oC

: The unit (J) are correct for heat. The sign of q is positive, as it should be since
absorbed heat from surrounding.

Energy
Energy is define as the ability to do work.
Work is done when a force is exerted through a distance.

Force through distance; work is done.

Energy is measured in Joules (J) or Calories (cal).
1 J = 1 kg m2 s-2
Energy may be converted from one to another, but it is neither
created nor destroyed (conversion of energy).
In generally, system tend to move from situations of high
potential energy (less stable) to situations having lower energy
(more stable).

Unit of Energy
A calorie (cal) is the amount of energy needed to raise the
temperature of 1 g of water by 1C.
1 cal = 4.184 J
The nutritional unit Calorie (Cal) is actually a kilocalorie (kcal):
1 Cal = 1000 cal = 1 kCal = 4184 J

Potential and Kinetic Energy

Kinetic energy (EK) is the energy due to the motion of
an object with mass m and velocity v:
EK = mv2
Thermal energy, the energy associated with the
temperature of an object, is a form of kinetic energy, because it
arises from the vibrations of the atoms
and molecules within
the object.
Potential energy (EP) is energy due to position, or any
other form of stored energy. There are several forms of
potential energy:
Gravitational potential energy
Mechanical potential energy
Chemical potential energy (stored in chemical bonds)

Internal Energy
The internal energy, U of a system is the sum of the kinetic
and potential energies of all the particles that compose the
system or the total energy of a system.
Internal energy is the state function, which means that its
value depends only the state of the system, not the how
the system arrive at the state.
Some
examples
include
energy
(and
many
other
thermodynamic terms), pressure, volume, altitude, distance, etc.
An energy change in a system can occur by many different
combinations of heat (q) and work (w), but no matter what
the combination, U is always the same the amount of
the energy change does not depend on how the change
takes place.

U = q + w

titude is a state function. The change in altitude during climbing depends only o
the difference between the final and initial altitudes.

Example: reaction between carbon and oxygen to form

carbon dioxide
C(s) + O2 (g)
CO2(g)
In this reaction, energy is released from the system to the
surroundings.
The reactants have a higher E than the products, so U for the
system is negative.
This energy is gained by the surroundings, where U is
positive.
(Usystem = -Usurroundings)

U < 0
(negative)

System
Usys

Surrounding
s

Energy flow
Usurr > 0 (positive)
< 0 (negative)

If the reaction is reversed, energy is absorbed by the system

from the surroundings.
The reactants have a lower E than the products, so U for the
system is
positive.
This energy is lost by the surroundings, where U is negative.

U > 0
(positive)

difference , U is positive and energy glows into the system and out of
surroundings

System
Usys

Surrounding
s

Energy flow
Usurr < 0 (negative)
> 0 (positive)

rizing:

reactants have a higher internal energy than a products, Usys is neg

energy flows out of the system into the surroundings.

reactants have a lower internal energy than a products, Usys is posi

gy flows into the system from the surroundings.

A system can exchange energy with its surroundings through heat and work:
Heat (q)

System

Work (w)

Surroundin
gs

ng to the first law thermodynamic, the change in the internal energy of the s
ust be the sum of the heat transferred (q) and the work done (w):

U = q
+w
q (heat)
w (work)
U
(change in
internal

Sign of conventions for q, w, and U

+ system gain thermal
- System loses thermal
energy
energy
+ work done on the
system

- Work done by the

system

+ energy flows into the

system

- Energy flows out of the

system

 For an isolated system, with no energy flowing in or out of

the system, the internal energy is a constant.
First Law of Thermodynamics (restated): The total
internal energy of an isolated system is constant.
It is impossible to completely isolate a reaction from its
surroundings, but it is possible to measure the change in the
internal energy of the system, U, as
energy flows into the system from the surroundings or flows
from the system into the surroundings.

U = Uf - Ui

Enthalpy
Most reactions are not done in sealed containers: they are carried
out in open vessels at constant pressure, with the volume capable of
changing freely, especially if the reactants or products of the reaction
involve gases.
In these cases, V 0, and the energy change may be due to both
heat transfer and PV work.
In order to eliminate the contribution from PV work, a quantity called
enthalpy, H, is defined as internal energy (U) plus the product of
H=U+
pressure and volume:

pV

p: pressure, V:volume
Because p,V,U are all state function, the enthalpy is a state function
Htoo.
=
qP
The change in enthalpy (H) is:

e Measurement of Enthalpy Chan

orimeter
itoring the temperature change that accompanies a physical or chemical change
curring at constant pressure.
ample: thermally insulated vessel open to the atmosphere: the heat released in
action is monitor by measuring the change in temperature of the content.
mb Calorimeter
Measuring the internal energy change.

Hm = Um +pVm
Um
erential Scanning Calorimeter
most sophisticated way to measure enthalpy changes.

Example 3:
When 2.0 mol CO2 is heated at the constant
pressure of 1.25 atm, its temperature
increase from 250 K to 277K. Given the
molar heat capacity of CO2 at constant
pressure is 37.11JK-1, calculate q, H and U.

Adiabatic Changes
The change in internal change of a
perfect gas when the temperature is
change from Vi to Vf.
Step 1:
The
volume
changes
and
the
temperature is constant at its initial
value. The system expands at the
constant temperature; there is no
change in internal energy if the system
consist of a perfect gas.
Step 2:
The temperature of the system is
reduced at constant volume.
Because the expansion is adiabatic, we know that q = 0; because
U=q + w , it then follows that U = wad. Therefore, by equating the
two expansion we have obtained for U we obtained

Wad = Cv
T

Renungan:
Termodinamik merupakan satu subjek yang aneh. Kali pertama anda
mempelajarinya,
anda tidak faham langsung. Kali kedua anda mempelajarinya, anda fikir
anda memahaminya
kecuali satu dua perkara. Kali ketiga anda mempelajarinya, anda tahu
bahawa anda tidak
memahaminya, akan tetapi anda sudah terbiasa dengan subjek itu maka
subjek itu tidak
akan menjadi masalah lagi kepada anda
Arnorld Sommerfeld (1868-1951)

PART 2: FIRST LAW THERMODYNAMIC

THERMOCHEMISRT
Y

Thermochemistry: Basic
Terms
Thermochemistry is the study of
energy changes that occur during
chemical reactions.
System: the part of the universe
being studied.
Surroundings: the rest of the
universe.

Types of systems:
open (exchange of mass and energy)
closed (exchange of energy)
isolated (no exchange)

Open
system

Close
System

Isolated
system

Types of Systems
Open: energy and
matter can be
exchanged with the
surroundings.
Closed: energy can
be exchanged with
the surroundings,
matter cannot.
Isolated: neither
energy nor matter
can be exchanged
with the
surroundings.

A closed system;
energy (not matter)
can be exchanged.

After the lid of the jar

is unscrewed, which
kind of system is it?

ENTHALPY (H)
The energy possessed by a system is
called the enthalpy or heat content of
the system and is given the symbol H.
The change of the heat content is given
by H,
H = Hfinal - Hinitial
H = Hproduct - Hreactant

Heat (q)
Heat is energy transfer resulting from thermal
differences between the system and surroundings
flows spontaneously
from higher T
lower T
flow ceases at
thermal equilibrium
EOS

Enthalpy(H) vs heat (q)

When reactions take place at
constant pressure;
heat change = enthalpy change

= H

The quantity of heat energy liberated or

absorbed during a reaction taking place at
constant pressure is the enthalpy change
of the reaction.

Exothermic reaction
A chemical reaction that
releases/gives off heat is called an
exothermic reaction
During an exothermic process, heat
flows
out of the system and into the
surrounding.
Thus the energy of the system is
negative.
Eg : C(s)

H = -ve
+ O2(g)

CO(g) H = -393.5

Exothermic Reaction
Surroundings are at 25 C

25 C

Typical situation:
some heat is released
to the surroundings,
some heat is absorbed
by the solution.

Hypothetical situation: all heat

is instantly released to the
surroundings. Heat = qrxn

32.2 C

35.4 C

In an isolated system, all heat is

absorbed by the solution.
Maximum temperature rise.

Endothermic reaction
A chemical reaction that
absorbs/takes in heat is called an
endothermic reaction.

During an endothermic process,

heat flows into the system from
the surrounding.
Thus the energy of the system is
positive.
H = +ve

Internal Energy Change at

Constant Volume
For a system where
the reaction is
carried out at
constant volume,
V = 0 and U = qV.
All the thermal
energy produced by
conversion from
chemical energy is
released as heat; no
P-V work is done.

lnternal Energy Change at

Constant Pressure
For a system where the
reaction is carried out
at constant
pressure,
U = qP PV

or

Most of the thermal

U + PV = qP
energy is released as
heat.
Some work is done to
expand the system
against the
surroundings (push
back the
atmosphere).

Enthalpy and Enthalpy

Change
Enthalpy is the sum
of the internal energy
and the pressurevolume product of a
system:
H = U + PV
For a process
carried out at
constant pressure,
qP = U + PV
soqP = H

The evolved H2
pushes back
the
atmosphere;
work is done at
constant
pressure.

Mg + 2 HCl MgCl2
+ H2

Most reactions occur at

constant pressure, so for most
reactions, the heat evolved
equals the enthalpy change.

Enthalpy Diagrams
Values of H are measured
experimentally.
Negative values indicate exothermic
reactions.
Positive values indicate endothermic
reactions.

A decrease in enthalpy
during the reaction;
H is negative.

An increase in enthalpy
during the reaction;
H is positive.

Thermochemical
Equations

A themochemical equation is an equation

that represents a reaction and shows the
overall enthalpy changes during the
reaction.
The following are three important rules for
writing thermochemical equations:
1. The physical states (s, l, g) of all
reactants
and products must be specified.
2H2O(l)
2H2O(g) H= 88.0
kJ/mol

2. When both sides of a thermochemical

equation is multiplied by a factor, then
H must also be multiplied by the same
factor.
H2O(s)
kJ/mol
2H2O(s)
kJ/mol

H2O(l) H= 6.01
2H2O(l) H= 12.02

3. When a chemical equation is reversed,

the value of H is reversed in

Reversing a Reaction

H changes sign when a process is

reversed.
Same magnitude; different signs.

ENTHALPY OF REACTION
Standard enthalpy of a reaction is
the enthalpy change for a reaction in
which the reactant in their standard
states yield products in their
standard states.
Enthalpy measured at this condition
is called STANDARD ENTHALPY OF
REACTION and is written as H

STANDARD STATES/
CONDITIONS

Temperature fixed at 25 oC or 298 K

Pressure fixed at 1 atm or 101 kPa
Concentration of solution is 1 M
Physical states of reactants and
products
are specified (s, l, g, aq)
H2(g) + O2(g)
kJ/mol
H2(g) + O2(g)
kJ/mol

H2O(g) H = -241
H2O(l) H = -286

TYPES OF ENTHALPY OF
REACTION
STANDARD ENTHALPY OF FORMATION Hf
STANDARD ENTHALPY OF COMBUSTION

Hc

STANDARD ENTHALPY OF NEUTRALIZATION

Hn
STANDARD ENTHALPY OF SOLUTION

Hsoln

Standard Enthalpies of
Formation
It would be convenient to be able to use the simple
relationship
H = Hproducts Hreactants

to determine enthalpy changes.

Although we dont know absolute values of enthalpy, we
dont need them; we can use a relative scale.
We define the standard state of a substance as the state
of the pure substance at 1 atm pressure and the
temperature of interest (usually 25 C).
The standard enthalpy change (H) for a reaction is
the enthalpy change in which reactants and products are in
their standard states.
The standard enthalpy of formation (Hf) for a
reaction is the enthalpy change that occurs when 1 mol of
a substance is formed from its component elements in
their standard states.

Calculations Based on
Standard Enthalpies of Formation
Hrxn = p x Hf(products) r x Hf(reactants)

The symbol signifies the summation of

several terms.
The symbol signifies the stoichiometric
coefficient used in front of a chemical symbol
or formula.
In other words
1. Add all of the values for Hf of the products.
2. Add all of the values for Hf of the
reactants.
3. Subtract #2 from #1

STANDARD ENTHALPY OF FORMATION Hf

Is the enthalpy change when one

mole of compound forms from its
elements in their standard states
(298 K, 1 atm)
CO2(g) Hf =-394
C(s) + O2(g)
kJmol-1
H2O(l) Hf = H2(g) + O2(g)
296kJmol-1
NaCO3(s)
Na(s) + C(s) + 3/2O2(g)

 1 mole of compound formed from the

most stable form of its element:
C(s) + O2(g)
CO2(g) Hf =-394
kJmol-1
element C exists naturally as solid
atom
element O2 exists as molecule in
gaseous form. They do not need to
be formed. Thus the enthalpy of
formation of this element is given
zero :

STANDARD ENTHALPY OF COMBUSTION

Hc

Is the enthalpy change when 1 mole

of a substance is completely burnt in
excess oxygen under standard
conditions:
i) CH4 (g) + 2O2(g)
CO2(g) + 2H2O(l) Hc = -45
kJ/mol
ii) Mg(s)
+ O2(g)
MgO(s) Hc = -165
kJ/mol
iii) CH3OH(g) + 3/2O2(g)
CO2(g) + 2H2O(l) Hc =
-715 kJ/mol

Standard enthalpy of
neutralization
Is the enthalpy change when 1 mole
of water formed from the reaction
between 1 mole of H+ and 1 mole
of OHHCl + NaOH

H2O + NaCl

Hn =-57 kJ/mol
The neutralization of any strong acid by
any strong base gives about the same
value ie ~ 57 kJ/mol

Standard enthalpy of
solution
Is the enthalpy change when 1 mole
of substance is completely
dissolved in water.
NaOH

(s)

NaNO3(s)

Na+(aq) + OH-(aq)
Na+(aq) + NO3- (aq)

How to determine Hrxn

1. Direct method (calorimetry exp)
2. From data of enthalpy of formation
3. Using Hesss law
4. Thermochemical cycle

How to measure enthalpy

change
1. DIRECT METHOD ( through
experiment)

Calorimetry
Heat absorb or evolve is measured
using a calorimeter
Two types of calorimeter :
Coffee-cup calorimeter
Bomb calorimeter

Calorimetry
Calorimetry is a technique used to measure heat
exchange in chemical reactions
Calorimetry measuring the heat
flow associated with a chemical
reaction by measuring the
temperature.

EOS

Calorimetry
We measure heat flow using
calorimetry.
A calorimeter is a device used to
make this measurement.
A coffee cup calorimeter may be
used for measuring heat involving
solutions.
A bomb calorimeter is used to
find heat of combustion; the
bomb contains oxygen and a
sample of the material to be
burned.

Calorimetry, Heat Capacity,

Specific Heat
Heat evolved in a reaction is absorbed by the
calorimeter and its contents.
In a calorimeter we measure the temperature
change of water or a solution to determine the heat
absorbed or evolved by a reaction.
The heat capacity (C) of a system is the quantity of
heat required to change the temperature of the system
by 1 C.
C = q/T (units are J/C)
Molar heat capacity is the heat capacity of one mole
of a substance.
The specific heat (s) is the heat capacity of one gram
of a pure substance (or homogeneous mixture).
s = C/m = q/(mT)
q = s m T

Heat Capacity: A Thought

Experiment
Place an empty iron pot weighing 5 lb on
the burner of a stove.
Place an iron pot weighing 1 lb and
containing 4 lb water on a second
identical burner (same total mass).
Turn on both burners. Wait five minutes.
Which pot handle can you grab with your
bare hand?
Iron has a lower specific heat than
does water. It takes less heat to warm
up iron than it does water.

How does a calorimeter

measure heat (q)
Heat evolved in a reaction is
absorbed by the calorimeter and its
contents (water or solution).
In a calorimeter the temperature
change of water or a solution is
measured to determine the heat
absorbed or evolved by a reaction.

specific heat capacity

The specific heat capacity (or
specific heat) is the heat required
to raise the temperature of 1 gram of
a substance by 1 oC.
Specific heat capacity of water :
4.184 J /(g oC).
4.184 J energy is needed to raise the
temperature of 1 g of water b 1 oC

TO CALCULATE q
q is calculated using
q = mass x specific heat capacity
x T

q = m c T

If T is positive (temperature
increases), q is positive and heat is
gained by the system.
If T is negative (temperature
decreases), q is negative and heat
is lost by the system

Calculation of q example
Calculate the heat absorbed when the
temperature of 15.0 grams of water
is raised from 20.0 oC to 50.0 oC.
(The specific heat of water is 4.184
J/g.oC.)
using the equation q = mc T
T = (50oC 20oC ) = 30oC,
therefore
q = 4.184 x 15 x 30 = 188.28 J
= 1.88 kJ

Calculating enthalpy using

direct method
When 23.6 grams of calcium
chloride, CaCl2, was dissolved in 500
mL water in a calorimeter, the
temperature rose from 25.0 oC to
38.7 oC.
Given the heat capacity of water is
4.18 J/g oC, and density of water is 1
g/mL, what is the enthalpy
change per mole of calcium
chloride?

Heats of Reaction:
Calorimetry

First, calculate the heat absorbed

by the calorimeter.
q = mc T
q= 500 g x 4.18 J/g oC x (38.725) oC
q= 28633 J = 28.633kJ
Now we must calculate the heat per mole
of calcium chloride.

Heats of Reaction: Calorimetry

Calcium chloride has a molecular
mass of 111.1 g, so
(1 mol CaCl 2 )
( 23.6 g CaCl 2 )
0.212 mol CaCl 2
111 .1 g
Now we can calculate the heat per mole of
calcium chloride.
qrxn
28.633 kJ
H

135.06 kJ / mol
mol CaCl 2
0.212 mol

Calculating Hn by
calorimetry
25.0 cm3 of 1.00 M HCl at 21.5oC were
placed in a polystyrene cup and 25.0 cm3
of 1.00 M NaOH at 21.5oC was added.
The mixture was stirred, and the
temperature rise to 28.2oC. The density
of each solution = 4.18J/(K g). Calculate
the
standard
molar
enthalpy
of
neutralization.

1. calculate
using
q heat
mcchange
T

q= mct
= 50.0 g x 4.18 J/(K g) x 6.7 OC= 1400 J
= 1.4 kJ
2. Calculate heat change per mole (Hn )
mole of H2O formed in the reaction=
25.0 x10-3 dm3 x 1.0 M = 2.5 x10-2 mol
2.5 x10-2 mol H2O formed = 1.4 kJ
1 mol H2O formed =

x 1.4

2.5 x10-2 mol

= 56 kJ/mol

2. Calculating enthalpy using data

from Standard Enthalpies of Formation

The law of summation of heats

of formation states that the
enthalpy of a reaction is equal to the
total formation energy of the
products
minus
that
of
the
reactants.
H o nH of (products ) mH of (reactants )
is the mathematical symbol meaning the
sum of, and m and n are the coefficients of the
substances in the chemical equation.

Using Hf to calculate enthalpy of reaction

Calculate the enthalpy of reaction

for the following reaction:
2Al(s) + Cr2O3(s)
Cr(s)

Al2O3(s) + 2

given Hf (Cr2O3(s)) = -1669 kJ/mol

Hf (Al2O3(s)) = -1128 kJ/mol

Using Hf to calculate
Hrxn
2Al(s) + Cr2O3(s)
Cr(s)
Hf = 0
=0

Hf = -1669

Al2O3(s) + 2

Hf = -1128

Hf

Hrxn = of Hf of products - of Hf of
reactants
= [2(0) + (-1128)] [(-1669) + 2(0)]
= 541 kJ/mol

Hesss Law
Hesss law states the enthalpy change of a reaction is
constant whether the reaction is carried out directly in one
single step or indirectly through a number of steps.
System A

H1

H4

System B

H2
H3

System
A

System
A

Example 1 : Hesss law

Hydrogen iodide can be prepared from
hydrogen and iodine using two separate
routes.
Route I:
Eqn 1:
H2(g) + I2(s) 2HI(g)
H =
+52.1 kJ
Route II:
eqn 2: I2(s) I2(g)
H=
+61.3 kJ
eqn 3: H2(g) + I2(g) 2HI(g) H= -9.2 kJ

Eqn 1 can be obtained when eqn 2 is added to eqn

3; eqn 1 = eqn 2 + eqn 3
eqn 2: I2(s) I2(g)
eqn 3: H2(g) + I2(g) 2HI(g)
H2(g) + I2(s) 2HI(g

H= +61.3 kJ
H= -9.2 kJ

Hence H1 = H2 + H3
= 61.3 9.2 = +52.1 kJ
The total enthalpy change for the route I is the
same as that for route II.

Hesss Law
Example 2; H for formation of SO3 cannot
be obtained directly but the enthalpy of
these reactions are known:
o

S(s ) O 2 (g ) SO 2 (g ); H -297 kJ
o
2SO 3 (g ) 2SO 2 (g ) O 2 (g ); H 198 kJ
The above data can be used to obtain the
enthalpy
change for the formation of SO3 according to
o
the
2S(s ) 3O 2 (g ) 2SO 3 (g ); H ?
following reaction?

 The third equation can be obtained by

multiplying the first equation by 2 and
added to the reverse of the second
equation, they will sum together to
become the third.

2S(s ) 2O 2 (g ) 2SO 2 (g ); H o (-297 kJ) (2)

2SO 2 (g ) O 2 (g ) 2SO 3 (g ); H o (198 kJ) (-1)
o

2S(s ) 3O 2 (g ) 2SO 3 (g ); H -792 kJ

exercise

Determine the heat of reaction;

Fe2O3(s) + FeO(s)
Fe3O4(s)
Using the information below:
i) 2Fe(s) + O2(g)
2FeO(s) Ho = -554.0
kJ
ii) 4Fe(s) + 3O2(g)
-1648.8 kJ
iii) 3Fe(s) + 2O2(g)
-1118.4 kJ
(Answer : -22.0 kJ)

2Fe2O3(s) Ho =
Fe3O4(s) Ho =

Thermochemical cycle / energy diagram

Reactant ( A + B)
route 2

Ho2
route 1

Ho
route 3

Product (C + D )

Ho3

Enthalpy diagram illustrating

Hesss law.

Hesss Law: An Enthalpy

Diagram
We can find H(a) by
subtracting H(b) from H(c)

Born Harber cycle

Born Haber cycle is an energy cycle
used to calculate the lattice energy
which cannot be obtained by direct
experimental method. They only can
be obtained by applying Hesss law
in this cycle which involving breaking
and forming bonds.

 Lattice energy
The enthalpy change when one mole
of
ionic compound (crystalline substance)
is
formed from its gaseous ions.
Na+(g) + Cl-(g)
kJ/mol
2Al3+(g) + 3O2-(g)
-1596 kJ/mol

NaCl(s)
Al2O3(s)

Hlat = -788
Hlat =

ii) Enthalpy of atomization

The enthalpy change when one mole of gaseous

atoms is formed from its elements under standard
conditions

Na(s)
O2(g)

H = +108 kJ/mol
H = +247 kJ/mol

Na(g)
O(g)

iii) Electron Affinity

The enthalpy change when one mole of

gaseous atom gains one mole of electron to
form anion.
O(g) + e-

O-(g)

H = -141.0 kJ/mol
(1st electron

affinity)
O-(g) + ekJ/mol

O2-(g)

H = -744.0

iv) Ionization Energy

The standard ionization energy is the enthalpy
required to remove one mole of electrons from one
mole of gaseous metallic atoms to form one mole
of positively charged ions. The process is
endothermic because energy is absorbed to
release electrons from an atom .
Mg(g) - e-

Mg+(g)

(1st ionization

energy)

Mg+(g) - eenergy)

Mg2+(g)

(2nd ionization

 Born haber cycle for LiF

Calculate the lattice energy for NaCl(s) using

the
following data.
a. standard enthalpy of formation of NaCl(s) Hf = -411kJ/mol
b. standard enthalpy of atomization of Na(s) Ha = +108 kJ/mol
c. first ionization energy of Na(s) HIE

= -+494 kJ/mol

d. standard enthalpy of atomization of Cl2(s)

e. first electron affinity of Cl2(g)

HEA

Hf

= +121 kJ/mol

= -364 kJ/mol

f. Standard lattice enthalpy of NaCl(s) Hlat

= x kJ/mol

Measuring Enthalpy Kirchhoffs Law

The standard enthalpy of many important reactions have been
measure at
Different temperatures.
However, in the absence of this information standard reaction
enthalpies at different temperature may be calculated from heat
capacities and reaction enthalpy at some at some other
temperature.
When temperature is increased, the
enthalpy of the products and
reactants both increase, but may do
so to different extent.
In each case, the change in enthalpy
depends on the heat capacities of
the substances.
The change in reaction enthalpy
reflects the difference in the
changes of the enthalpy.

When a substance is heated from T1 to T2, its enthalpy changes from H(T1) to
Eqn 1
Assumed that no phase transition take place
in the temperature range of interest) because
this equation applies to each substance in the
reaction the standard reaction, the standard
reaction enthalpy changes from Hr(T1) to

Kirchhoffs
Law
Eqn 2

here the
is the difference of the molar heat capacities of product and
eactants under standard conditions weighted by the stoichiometri coefficient tha
ppear in chemical equation:
Eqn 3

Example:

The standard enthalpy of formation of H2O (g) at 298K is 241.82kJ mol-1.

Estimate its value at 100oC given the following values of the molar heat capacitie
At constant pressure:
H2O (g) = 33.58JK-1mol-1
H2(g) = 28.82 JK-1mol-1
O2 = 29.36 JK-1 mol-1
Assume that the heat capacities are independent of temperature.

Method: When
is independent of temperature in the range T 1 to T2, the
ntegral in eqn 2 evaluate to (T2-T1)
. Therefore,

To proceed, write the chemical equation, identify the stoichiometri coefficients, an

Calculate
from the data.

Answer: The reaction is H2 (g) + O2 (g) H2(g), so

It then follows that

State Function
and
Exact Differentials

e internal energy and enthalpy are two example of state functions.

ysical quantities that do depend on the path between two state are called
th function.

ample of path functions are the work and the heating that are done when
eparing a state.
do not speak of a system in a particular state as possessing work or heat.

each case, the energy transferred as work or heat relates to the path being
ken between states, not the current state itself.

part of the richness to thermodynamic is that it uses the mathematical properties

state functions to draw far-reaching conclusions about the relations between
ysical properties and thereby establish connections that may be completely
expected.

e practical importance of this ability is that we can combine measuremen

fferent properties to obtain the value of a property we required.

Exact and Inexact

Differentials
Work is done by
the system as it
expands
adiabatically to a
state f.
In these state the
system has an
internal energy Uf
and the work done
on the system
along Path 1 from I
to f of is w.

Initial
state of
the
system
Initial and final
state are the
same as those in
Path 1 but in
which expansion
is not adiabatic.

Initial and final

states are the
U: property of the state, w=property of the pathsame as before
(because U is the
state funtion).
However, in the second path an energy q enter
the system as heat and the work w is not the
same as w. The work and the heat are path
functions.

f a system is taken along a path (for example, by heating it) U changes from U i
o Uf, and overall change is the sum (integral) of all the infinestimal changes alon
he path:
Eqn 4

e value of U depends on initial state and final state of the system but is
dependent of the path between them.

exact differential is an infinestimal quatity that when integrated gives a resul

at is independent of the path between the initial and final state.

hen the a system is heated the total energy transferred as heat is the sum of all
dividual contributions at each point of the path:
Eqn 5

Inexact differential is an infinitesimal quantity that, when integrated

gives a result that depends on the path between the initial and
final state.

differences between Eqn 4 and Eqn 5:

We do not write q because q is not a state function and energy supplied as heat
annot be expressed as qf-qi.
We must specified the path of integration because q depends on the path selecte
example: and adiabatic path has q=0, whereas on the non-adiabatic path betwe
he same two state would have q0).

eneral, an inexact differential is an infinestimal quantity that, when integrated,

es a result that depends on the path between the initial and final state.

work done on a system to change it from one state to another depends on the
h taken between the two specified states.
example: in general the work is different if the change takes place adiabatically a
non-adiabatically. It folows that dw is an exact differential.

Changes in Internal
Energy
In internal energy U can be regarded as a function of V,T, and p, but because

there is an equation of state, stating the values of two of the variables fixes the
value of the third.
Therefore, it is possible to write U in terms of just two independent variables:
V and T, p and T, or p and V.
Expressing U as a function of volume and temperature fits the purpose of our
discussion.

General expression for a change in U with T and

V
Eqn 6

Definition of internal pressure

Eqn 7

In terms of the notification Cv and

,eqn 5 can now write as

Eqn 8

The Joule Experiment

James Joule thought that he could measure
by observing the chenge in
Temperature of a gas when it is allowed to expand into vacuum.
When the stopcock opened
and the air expanded into a
vacuum.

Filled with air

at about 22
atm

No change in
temperature

A schematic diagram of the apparatus used

by Joule in an attempt to measure the
change in internal energy when a gas
expands isothermally. The heat absorbed by
the gas is proportional to the change in
temperature of the bath.

The implication as follow:

1. No work was done in the expansion into a vacuum, so w=0.
2. No energy entered of left the system (the gas) as heat because the
temperature of the bath did not change, so q = 0. Consequently,
within the accuracy of the experiment, U=0.
Joule concluded that:
U does not change when a gas expand isothermally and therefore that
=0.
His experiment, how ever is crude.
The heat capacity of the apparatus was so large that the
temperature change that gases do in fact cause was too small
to measure.
Nevertheless, from his experiment Joule had extracted an essential
limiting property of a gas, a property of a perfect gas, without a
small deviations characteristic of a real gas.

hanges in Internal Energy at Constant Pressure

As an example, suppose we want to find out how the internal energy
varies with temperature when the pressure rather than volume of the
system is kept contant.
If we divided both sides of eqn 8 by dT and impose the condition of
constant pressure on the resulting differentials, so that du/dT on the
left becomes
(U/ T)p we obtain:
Eqn 9
It is usually in thermodynamic to inspect the output of a
manipulation like this to see if it contains any recognizable physical
quantity. The partial derivative on the right in this expression is the
slope of the plot of volume against temperature (at constant
pressure). This property is normally tabulated as the expansion
coefficient, , of a substance, which is defined as:
Definition of
Eqn 10

the expansion
coefficient

A large value of means that the volume of the sample respond

strongly to changes in temperature.

List some experimental values of

Isothermal compressibility, KT( kappa) which define as

Eqn 11

sothermal compressibility is a measure of the fractional change in a volume

when the pressure is increase by a small amount; the negative sign in definition
nsure that the compressibility is positive quantity; because an increase of
ressure, implying a positive dp, bring about reduction of volume, a negative dV.

The Joule-Thompson
The closed system of constantEffect
composition
Eqn 12

Where the Joule-Thompson coefficient, (mu) is define as

Eqn 13

This relation will prove useful for relating the heat capacities at constant volume
and for a discussion of liquefaction of gases.

Observation of the Joule-Thompson Effec

he analysis of the Joule-Thompson coefficient is central to the technological

roblems associate with the liquefaction of gases. We need to be able to interpre
s physical and measured it.
The apparatus used to for
measuring
The Joule-Thompson effect. The gas
Expands through the porous barrier,
Which acts as a throttle, and the
whole
apparatus is thermally insulated.
This arrangement corresponds to an
Isenthalpic expansion
(expansion at constant enthalpy).
Whether the expansion results in a
heating
or a cooling of the gas depends on
the
conditions

Definiton of the
isothermal JouleThompson
coefficient

The isothermal Joule Thompson

coefficients is the slope of the
enthalpy
with respect to changing pressure
the temperature being held
constant.
By compressing Eqn 12 and above equation, we can see that the two
coefficients are related by

A schematic diagram of the apparatus used for measuring the

isothermal Joule-Thompson coefficient. The electrical heating
required to offset the cooling arising from expansion is
interpreted as H and used to calculate
, which is then
converted to .

Real gases have nonzero Joule-Thompson

coefficient. Depending on the identity of the
gas, pressure, the relative magnitudes of the
attractive and repulsive intermolecular forces,
and the temperature, the sign of the coefficient
may be either positive or negative.
+ve sign dT is ve when dp is ve
(in which case the gas cool on expansion)
Heating effect (<0) at one temperature
show at cooling effect (>0) when the
temperature is below their upper inversion
temperature,T1.

A gas typically has two

inversion
temperatures, one at high
temperature and the other at
low.

The principle of Linde refrigerator

The gas at high temperature is allowed to expand through a
throttle, it cools and is circulated past the incoming gas.
That gas is cooled, and its subsequent expansion cools it still
further.

THANK YOU