“Thermodynamics” is that branch of physical

chemistry which takes into account the

transformation among
ENERGY HEAT WORK

Classical Thermodynamics: independent of internal

constitution of matter.
Statistical Thermodynamics: relates atomic and bulk
properties of matter.
Thermodynamics

Thermo Electro Bio

Chemistry Chemistry energetics
• The useful generalization on which the very
existence of universe lies:
“ Law of Conservation of Energy”
“The total energy of a system and its surroundings
must remain constant, although it may be changed
from one form to the other”.
System: That part of world in which the study of
special interest is carried out.
Surroundings: Rest part of the universe except
the system.
(P,V,T,n)sorr ≈ Constant, i.e. Δ(P,V,T,n)sorr = 0
• Open system: exchange of both energy and matter
with its surroundings e.g. a living cell.
• Closed system: exchange of energy but not matter
with its surroundings e.g. a stoppered flask.
• Isolated system: can exchange neither matter nor
energy with its surroundings e.g. a sealed flask
insulated thermally, mechanically and electrically.
Work and Heat:
.
Work: Transfer of energy against an opposing
force. e.g. Mechanical work = P. ΔV
Electrical work = q × V = It × IR
= I2Rt in Joules.
Heat: Transfer of energy as a result of
temperature difference.
Walls that permit heating as a mode of transfer of
energy → Diathermic
Walls that do not permit heating as a mode of transfer
of energy → Adiabatic
Zn(s) + 2 HCl (aq) →ZnCl 2(aq) + H2(g) + Δ

Example of energy leaving a

System as work.

Molecular nature of work

suggests that, when weight
is raised in the surroundings
All atoms move in the
Same direction.
Work is the transfer of energy
that causes uniform motion
of atoms in the surroundings.

Heat is the transfer of energy

that causes chaotic motion
of atoms in the surroundings.
• A process in a system that heats the
surroundings i.e. heat is released to the
surroundings → Exothermic
Ex: All combustion reactions

• A process in a system that is heated by the

surroundings i.e. heat is absorbed from the
surroundings → Endothermic
Ex: Dissolution of NH4NO3 in water.
Measurement of Work
Work needed to raise the mass ( ) through
a height on the surface of earth is
Work = g
When a system does work the energy
transferred, , is a (−ve) quantity.
e.g. = − 100J.
When work is done on the system, the energy
transferred from surrounding to system, thus
is a (+ve) quantity.
e.g. = +100J.
 Expansion work: When a system expands through
a volume ΔV against a constant external pressure
the work done is
=− ΔV
The force opposing the
expansion is the external
Pressure multiplied by
the area of piston
Work done by the system
distance moved ×
opposing force
= × ( Α) = × ( A) = ΔV
Sign convention predicts =− ΔV
 Magnitude of determines the amount of
work a system does during expansion.
Iff, = 0, = 0. i.e. the system
does no work as it expands.
“Free expansion”
i.e. Expansion against zero external pressure.
▶ The work done by a chemical reaction at specified
T & P is calculated using perfect gas law.
nfRT/pex niRT/pex
ΔV = Vf – Vi = RT (Δng / pex)
∴ =− ΔV = − x RT (Δng / pex) = − RT. Δng
If, the reaction results in the net production of gases,
then Δng > 0 and w < 0; conversely, net consumption
of gases Δng < 0 and w > 0.
Self-test
Calculate the work done by a system in which a
reaction results in the formation of 1.0 mol CO2(g)
treated as perfect gas at 25oC and 100kPa.
= − (8.3145 J K-1 mol-1) x (298 K) x (1 mol)
= − 2.5 x 103 J = − 2.5 kJ
Self-test 2.1
Determine the work done when 1.0 mol of propane
gas molecules react with O2 to produce CO2 and liquid
water at 25oC
C3H8(g) + 5O2(g) ---- 3CO2(g)+ 4 H2O(l) Ans: +7.4
Q-2- Determine the work done when 1.0 mol of butane gas
molecules react with O2 to produce CO2 and liquid water at
25oC
The work obtained is minimum if sys and
are significantly different.
Maximum work obtained iff,
sys = ex + δ

A system that remains in mechanical

equilibrium
with its surrounding at all stages of the
expansion
does maximum expansion work.
• If the pressure of surrounding is made
infitesimally higher than the system: lead to
compression (change in opposite direction)
i.e. ex = sys + δ
Any change that can be reversed by an
infitesimal change in a variable
“Reversible Change”
To summarize, a system does maximum
expansion work, if
(i) ex ≈ at every stage of expansion
(ii) It is in mechanical equilibrium with its surr.
(iii) The change is reversible
 To ensure reversibility of a process, the ex
must be adjusted in the course of expansion.
Hence, it is assumed that the process taking
place in series of small steps called
“infitesimal steps”.
When the system expands through an infitesimal
volume dV, the infitesimal work, d , done is d =
− ΔV
If, ex ≈ P, then d = − ΔV

=− pd P = nRT/
 =− nRT/ d

For the isothermal, reversible expansion of a

perfect gas,

= −nRT d

or = −nRT ln f/ i
In an expansion f > i, hence, ln f / i = +ve.
So, W is (–ve). Energy leaves the system as
the system does expansion work.
• For a given change in volume,
Work done α temperature; At higher
temperature, the pressure of the gas is high, so
high ex to be used, hence a stronger opposing
force to match sys.
The work of reversible, isothermal expansion of a
perfect gas. For a given change of volume and
fixed amount of gas, the work is greater the
higher the temperature.
Self Test
Calculate the work done when 1.0 mol Ar(g)
confined in a cylinder of volume 1.0 dm3 at 25oC
expands isothermally and reversibly to 2.0 dm3.
Sol: We know = −nRT ln f/ i
= −1.0mol× 8.31447 J K-1mol-1× 298.15 K ln 2
= − 1.718 kJ.

Self Test 2A.2: Calculate the work done when 20g of

N2 gas is compressed isothermally from 2.0 dm3 to 1.
0 dm3 at 25oC.
Ans: + 1.227 kJ
Q-1: A sample of blood plasma occupies 0.550 dm3 at 0 0C
and 1.03 bar, and is compressed isothermally by 57 percent
by being subjected to a constant external pressure of 95.2
bar. Calculate the magnitude of the work done.
Volume of blood sample =0.55 dm3
T = 273 + 0 = 273 K
P= 1.03 bar Pex= 95.2 bar
Compressed by 57%
Therefore, 0.55 х 10-3 m3 х 0.57 =3.135 х 10-4 m3
ΔV = -3.135 х 10-4 m3
Pex = 95.2 bar or 95.2 х 105 Pa

∴W = -Pex ΔV
= -95.2 х 105 Pa х (-3.135 х 10-4) m3
= 2984.52 J = 2.98 kJ
Q-2: In an isothermal reversible compression of 52 mmol of
perfect gas molecules at 260 K, the volume of the gas is
reduced from 300 cm3 to 100 cm3. Calculate the magnitude
of
work done for this process.

n = 52 mmol = 52 х 10-3 mol

T= 260 K
Vi = 300 cm3
Vf = 100 cm3
W = - nRT ln f / i
= - 52х10-3 х 8.314JK-1mole-1 х 260 K х ln 100/300
= - 52х10-3 х 8.314JK-1mole-1 х 260K х (-1.098)
= + 123.4 J
Q-3 A strip of Mg metal of mass 12.5 g is dropped into a
beaker of dilute HCl. Given that Mg is the limiting reactant.
Calculate the work done by the system as a result of the
reaction. The atm pressure is 1.00 atm and temp is 20.2 0C .
Solution: Mg+ 2 HCl ----- MgCl2 + H2 (g)
Δ n for H2 = 1-0 = 1 mol
1 mole of Mg reaction with 2 moles of HCl to give 1 mole
Of H2
Now, n of Mg = 12.5/24.3 = 0.514 moles
T= 273+ 20.2 = 293.2 K
W= -Pex ΔV
Since ΔV = V V = nRT/P
W= -PexnRT/ Pex (as P is constant and equal to Pex)
W= -nRT = -0.514 х 8.314JK-1mole-1х293.2 = -1253 J = -1.253
kJ
Measurement of Heat
Mode (???)of energy transfer; for a specified energy,
, transferred by heating, the magnitude of
temperature change depends on the “heat
capacity” of substance.
q
C = ------- , i.e. q = c ΔT
ΔT

Ex: if the heat capacity of a beaker of water is

0.50 kJ K-1, and a temperature rise of 4.0K is
observed, heat transferred to water is
q = 0.50 kJ K-1× 4.0 K = 2.0 kJ
Why water requires more energy per gram of liquid
than oil to change its temperature?

Ans: Heat capacity of water is higher than oil.

Heat capacity is an extensive property (amount of

substance present) can be made intensive by
dividing with the mass of sample.
‘C’ as an intensive property called “specific
heat capacity”, Cs, or molar heat capacity, Cm.
– Specific heat capacity is often called
“C” of a substance depends on the condition
of sample.
Cv → Heat capacity at constant volume
Ex. A gas in sealed vessel
Cp → Heat capacity at constant pressure
Ex. Water in the open container

Ex: Cp,m of water is 75 JK-1 -1

mol .
What is the
temperature rise when 1.0kJ of energy is
supplied by heating to 100 gm of water.
Sol: ΔT = q / Cp = q / nCp,m= 1.0 × 103 J
-1
5.55 mol × 75 JK mol -1

= + 2.4 K
Calorimeter is the device to measure the energy
transferred as heat.
It is a thermally insulated device, records the rise in
temperature due to heat released in the process
occurring inside it.

The observed rise in temperature is used to calculate

the heat capacity of the calorimeter called
“Calorimeter constant”.

Self test
In an experiment to measure the heat released by the
combustion of a sample of fuel, the temperature rose by 2.78oC.
When a current of 1.12A from an 11.5V source flows through a
heater in the same calorimeter for 162sec, the temperature rose
by 5.11oC. What is the heat released by the combustion reaction?
The heat supplied during the calibration step is
q= t= 1.12A × 11.5V × 162 sec
= 2.086 kJ

The heat capacity of the calorimeter is

C= q / Δθ = 2 . 0 8 6 kJ/ 5 . 1 1 οC =
408 JoC-1

The heat output of the combustion is

q= C Δθ= 408 JoC-1 × 2.78oC = 1.1 kJ.
Heat influx during expansion
Consider a perfect gas undergoing isothermal
expansion.
• As temperature constant, Cmean same before
and after expansion so does Ek. i.e Etot
unchanged.
• As energy has left the system as work;
therefore, a compensating amount of energy
must have entered the system as heat.
Thus, q=−
or, q = nRT ln f/ i
Internal energy & Enthalpy
Heat and work (q & ) are the equivalent
amount of energy, that can be transferred
into/out of system.
Mechanical equivalence of heat
• Both the path functions are interconvertible.
Both the modes of energy are stored inside a
system as “ ”.
• Grand total of all energy components of all
atoms, ions and molecules in the system.
• A measure of energy reserve of system,
analogous to Gold reserve of a country.
• Internal energy (U) is an extensive property i.e. f(
size, quantity of substance in a system).
• Um = U/n is an intensive property.
• U can not be measured as absolute value, but the
change in U i.e. “ΔU” can be measured as a
function of or q.
hence, ΔU = +q
For a perfect gas, as the total energy of sample
remain same, hence, ΔU = 0.
• For isothermal expansion of a perfect gas,
ΔU = 0

U is independent of the volume it occupies.

• U is a state function - a change, ΔU, in the internal
energy between two states of a system is
independent of the path between them.
• For an isolated system, as it can neither do work nor
heat its surroundings, U is unchanged ⇒ ΔU = 0
“
” → Basis of First law.

“ I t is impossible to constr uct a per petual machine, which

would do wor k without continuous supply of energy”.
Ex: 2.3- Suppose in the course of an experiment
someone does 622 kJ of work on an exercise bicycle
and loses 82 kJ of energy as heat. What is the change
in
internal energy of the person? Disregard any matter
loss
by perspiration.
ΔU = w + q = (-622 kJ) + (-82 kJ) = - 704 kJ

Self test 2.4: An electric battery is charged by

supplying
250 kJ of energy to it as electrical work, but in the
process it loses 25kJ of energy as heat to the
surroundings. What is the change in internal energy of
• If a reaction is carried out in a constant
volume container, the system can do neither
expansion nor non-expansion work.
=0, ΔU = qV
To measure a change in internal energy, a fixed
volume calorimeter is used → Bomb calorimeter
The arrangement is adiabatic. Thetemperature
variation inside the calorimeter is adjusted by an
inbuilt thermostatting device.
The definition of heat capacity under constant volume
conditions is given by
CV = qV / ΔT = (ΔU / ΔT )V
The Enthalpy:
• Most of chemical and biological reactions are
allowed to take place in open vessel i.e. at constant
pressure, but at varied volume.
• Consider the thermal decomposition of 1.0 mol of
CaCO3(s) at 1 bar pressure. The increase in volume
is nearly 90 dm3 at 800oC on account of the CO2 gas
produced.
• The surrounding atmosphere must be pushed to
accommodate the increase in volume of CO2.
The system must perform expansion work .
• Thus, the heat, , supplied to bring about the
endothermic decomposition ≠ Change in internal
energy (ΔU).
• Some of the heat supplied to the system has leaked
back into the surroundings as .

• If the heat supplied to the system at constant

pressure is designated by a thermodynamic
property, ENTHALPY (H).

According to definition, H = U +
• As the work done is essentially a type of
expansion work,
Hence, H = U +
• A change in Enthalpy, ΔH (can be measured
experimentally)
ΔH = ΔU + Δ at constant p.
• Enthalpy is an extensive property. The property can
be made intensive by dividing with the amount of
substance.
viz. Molar Enthalpy , Hm = Um + pVm

The relation is valid for all substances.

For a perfect gas, pVm =
Hence, for a perfect gas: Hm = Um +
At 25oC, = 2.5 kJ mol-1.
So, the molar enthalpy of a perfect gas differs from
molar internal energy by 2.5 kJ mol-1.
Because, Hm− Um =
Because H is defined in terms of the state
functions ( & ) the enthalpy is a state
function. i.e. ΔH = Hf – Hi is independent of
path traversed.
Heat transferred at constant pressure
If a system open to the atmosphere is considered, its
pressure is constant and equal to the external
pressure ex.
ΔH = ΔU + Δ
ΔH = ΔU + Δ
We know, ΔU = + , with Δ

∴ ΔH = ( Δ ) Δ
 The change in enthalpy of a system can be
identified with the heat transferred to it at constant
pressure.

At constant pressure, no non-expansion work:

ΔH = , or more precisely, ΔH =

✓ An endothermic reaction, for which > 0, taking

place at constant pressure results in increase in
enthalpy of the system i.e. ΔH > 0.

✓ An exothermic reaction, for which < 0, taking

place at constant pressure results in decrease in
enthalpy of the system i.e. ΔH < 0.
The temperature variation of the enthalpy:
Like Internal energy, , the enthalpy of a
system also increases with temperature.
From the definition of heat capacity,
C = /ΔT
But, we know,
ΔH =
CP = (ΔH/ ΔT)P
Ex: The enthalpy of 100 gm of H2O is
o o
greater at 80 C than at 20 C.
 The enthalpy change to attain this
difference in temperature of 60oC at
constant pressure = Amount of energy
transferred as heat into the system.
So, ΔH = CP.ΔT
or ΔH = 4.18 JK-1gm-1× 60K × 100 gm
= +25 kJ
CP, is the slope of plot of enthalpy against
temperature of a system at constant
pressure. (non-linear; slope of the tangent
to the curve).
 Relation between Um and Hm for a perfect gas gives
clue to the relation between CP and CV.
We know, Hm − Um = RT

When the temperature increases by ΔT, the Hm

increases by ΔHm and the Um by ΔUm.
So, ΔHm − ΔUm = R.ΔT
By dividing both sides by ΔT,
ΔHm/ΔT − ΔUm/ΔT = R
But from the definition, CP,m = (ΔHm/ ΔT)P &
CV,m = (ΔUm/ ΔT)V
Hence, CP,m − CV,m = R
• Molar heat capacity of a perfect gas is
greater at constant pressure than at constant
volume.
• At constant volume, all the energy supplied as
heat to the system remain inside and the
temperature rise accordingly.
• But at constant pressure, some of the energy
supplied as heat escapes to surroundings in
the form of expansion work.
Either, CP or CV α 1 / ΔT
ΔT is higher under constant volume condition
than under constant pressure condition.
 CP > CV or CP,m > CV,m
Ex: For O2, CP,m = 29.1 J K-1 mol-1 and CV,m = 20.
8 J K-1 mol-1
CP,m − CV,m = 8.3 J K-1 mol-1 = R
 The molar heat capacity of water is 75.3 JK-1 mol-1 .
What energy is needed to heat 250 g of water (a cup
coffee, for instance) through 40 0C.

lution: Given Cm= 75.3 JK-1mole-1

ΔT = 40 0C = 40 K
Mass = 250 g
Mole wt of water = 18 g/mol
n = wt/mol wt.= 250/18 = 13.89 mol
q = n CPm ΔT
=13.89 mol х 75.3 J/K.mol х 40 K
= 41833 J or 41.833 kJ
Q-2- When 229 J of energy is supplied as heat to
3.00 mol Ar(g), the T of the sample increases by
2.55K. Calculate the molar heat capacities at
Constant volume and constant pressure of the gas.
Solution: Given n = 3 moles; q = 229 J
ΔT = 2.55 K But we know, Cv= q/ΔT
= 229/2.55 = 89.8 JK-1
For 3 moles Cv = 89.8 JK-1
For 1 mole, Cv,m = 89.8/3 JK-1= 29.93 JK-1mole-1
Now, Cp,m – Cv,m = R
Cp,m = Cv,m + R
= (29.93 + 8.314) JK-1mole-1
= 38 JK-1mole-1
Q-3-The heat capacity of air at RT and pressure is
approximately 21 JK-1mole-1. How much energy is required
to
raise the temperature at a room of dimension 5.5 m х 6.5 m х
3.0 m by 10 0C? If losses are neglected., how long will it take
a heater rated at1.5 kW to achieve that increase given that 1
W =1Js-1
Solution: Given Cp = 21 JK-1mole-1
Room dimension = 5.5 m х 6.5 m х 3.0 m
So, volume of the room = 107.25 m3 = 107.25 х 103 L
Therefore, no of moles of air = 107.25 х 103 L/ 22.4
L/mol
= 4.78 х 103 moles
q = n.Cp,m ΔT
= 4.78 х 103 moles х 21 JK-1mole-1 х 10 K
= 1003.8 х 103 J

t= q/IV = 1003.8 х 103 J/1.5 х 103J/s = 669 sec

Q-4- In an experiment to determine the caloric value of a
food,
a sample of the food was burned in an oxygen atmosphere
and the temperature rose by 2.89 0C . When a current of 1.27
A from a 12.5 V source flowed through the same calorimeter
for 157s, the temperature rose by 3.88 0C. What energy is
released as heat by the combustion?
Solution: Given I= 1.27 A ; V = 12.5 V ; t = 157 sec
ΔT = 3.88 0C = 3.88 K
we know q = I V t =1.27 х 12.5 х 157
C= q/ΔT = 1.27 х 12.5 х 157/3.88
ΔT for combustion = 2.89 K
q = C. ΔT
= (1.27 х 12.5 х 157 х 2.89)/3.88
= 1856 J = 1.85 kJ
 Q-5- The internal energy of a perfect gas does not
change when the gas undergoes isothermal
expansion from Vi to Vf. What is the change in
enthalpy?
Solution: ΔH = ΔU + PΔV

ΔH = ΔU + RT (for perfect gas PV= RT)

Here internal energy is not changed so,
ΔU= 0
And for isothermal process T constant.

Therefore, ΔH = RT
= 8.314 х 298
= 2.5 kJmol-1
Q-6- A sample of a serum of mass 25 g is cooled from
290 K to 275 K at constant pressure by the extraction
of 1.2 kJ of energy as heat. Calculate q and ΔH and
estimate the heat capacity of the sample.

Solution: ΔT = 290-275 K = 15 K

q = -1.2 kJ or 1.2х103 J

We know, at constant pressure ΔH = qp

ΔH = -1.2 х 103 J

Cp= ΔH/ ΔT

= -1.2х103/ -15 K

-1
Q-7- When 3 mol O2 (g) is heated at constant pressure of
3.25
atm. its temperature increases from 260 K to 285 K. Given
that the molar heat capacity of O2 at constant pressure is
29.4JK -1mol-1, calculate q, ΔH and ΔU.
Solution: n = 3 moles
P= 3.25 atm
ΔT = 285-260 K = 25 K

Cp,m = 29.4 JK-1mole-1

P = 3.25 atm = 3.25 х 101.325 kPa

q = n Cp,m ΔT
= 3 х 29.4 х 25
= 2205 J or 2.2 kJ

at constant pressure ΔH = qp

= 2.2 kJ
Now ΔH = ΔU + PΔV

ΔU = ΔH – PΔV
= ΔH – nRΔT
(as PV= nRT)

= 2205 J – (3 х 8.314 х 25)

= 2205- 623.55
= 1581.45 J or 1.58 kJ
2.5 = mgh
= 1kg × 9.81m sec-2 × 10m
= 98.1 kg m2 sec-2 = 98.1 J
on the surface of moon
= 1kg × 1.60m sec-2 × 10m
= 16.0 kg m2 sec-2 = 16.0 J
2.6 Mass of bird = 0.2 kg, h = 20 m
W = mgh = 0.2 kg × 9.81m sec-2 ×
20m
= 39 J

2.7 Mass of person = 65 kg, h = 4.0 m

W = mgh = 65 kg × 9.81m sec-2 × 4m
= 2.6 kJ
2.8 Centre of mass of a cylindrical column
of liquid lies halfway its length.
ρ = m/V m = ρ V where, V =
πr2h
m=13.6× 10-3 kg× 106 m-3× 3.14(0.5×
-2
10 m) 2

× 0.76m
= 0.811376 kg
Work done = mg(h/2)
= 0.811376 kg × 9.81m sec-2×
(0.76m/2)
= 3.024kg m2 sec-2 = 3.024 J
2.13 Vinitial = (100 cm2 × x cm) = 100x cm3
Vfinal = 100 cm2(x cm + 10 cm)
= 100x cm3 + 1000 cm3
Vf − Vi = 1000 cm3 = ΔV
Work done = − pex . ΔV
= − 100 kPa × 1000 cm3
3
= − 100 × 10 Pa × 1000 × 10 -6

m3
3
= − 100 Pa m = − 1.0 × 10 J2
2.14 Area of cross section of container = 55 cm2
Mass of piston = 250 gm.
Horizontally, if ΔL = 155 cm, ex = 105 kPa
ΔV = ΔL × A
Whorizontal = − 105 × 103 Pa × (55 × 155)cm3
= − 895.12 J
Vertically,
Wg= mgh=0.25 kg × 9.81m sec-2 × 155 ×
10-2m
= 3.80 J
Wvertical = Expansion work + Wg = − 898.92 J
2.15 nCH4 = 0.28 mol, Vi = 12.7 dm3 at 310K
Given, ΔV = 3.3 dm3 & ex = 30.0 kPa
W = − ex. ΔV
= − 30 × 103 Pa × 3.3 × 10-3 m3
= − 99 J
Under isothermal reversible condition,
W = − nRT ln f/ i
=− 0.28 mol × 8.314 JK-1mol-1 × 310K ×
ln(16/12.7)
= − 167.0 J
2.17 Volume of blood plasma, Vi = 0.55 dm3
at 273.15K and 1.03 bar.
Compressed by 0.57% of Vi.
3
ΔV = 0.55 dm × (0.57/100)
= − 0.003135 × 10−3 m3.
W = − 95.2 bar × − 0.003135 × 10 −3

m3
= −95.2 × 105Pa × −0.003135 × 10−3
m 3

= 0.299 kJ.