Unit Ii - Thermodynamics

Unit – II: THERMODYNAMICS
Contents
Thermodynamic Systems, State Functions, Thermal Equilibrium and Temperature, Work,

Internal Energy and Heat Transfer, Heat Capacity. Natural and Reversible Processes, Entropy
and Second Law, Entropy Changes in (a) accompanying change of phase, (b)isothermal and
(c) isobaric processes. Standard free energy change in chemical reactions. 1
Introduction
Thermodynamics is the science that deals with heat and work and those properties of
substance that bear a relation to heat and work.
More specifically, thermodynamics deals with
(a) Energy conversion and (b) the direction of change.
The principles of thermodynamics are summarized in the form of four laws known as zeroth,
first, second, and the third laws of thermodynamics.
The 0th law of thermodynamics deals with thermal equilibrium and provides a means of
measuring temperature.
The first law of thermodynamics deals with the conservation of energy and introduces the
concept of internal energy.
The second law of thermodynamics dictates the limits on the conversion of heat into work
and provides the yard stick to measure the performance of various processes. It also tells
whether a particular process is feasible or not and specifies the direction in which a process
will proceed. As a consequence it also introduces the concept of entropy.
The third law defines the absolute zero of entropy.
Definitions of thermodynamics
System: The part of the universe that we choose to study

(or) a quantity of matter or a region in space chosen for
study.
Surroundings: The rest of the universe. (or) mass or

region outside the system
Boundary: The surface dividing the system from the

surroundings. (or) The real or imaginary surface that
separates the system from its surroundings.
Dr. K. Chandramohan, Assistant Professor, Department of Chemistry, MITS, Madanapalle-517325

Chittoor Dist., AP. drkchandramohan@mits.ac.in
Type of systems
Open system: Both mass and energy can cross the selected boundary i.e. mass and energy
can transfer between the system and surroundings. Ex. an open cup of coffee
Closed system: Only energy can cross the selected boundary i.e. energy can transfer between 2
the system and surroundings but not mass. Ex. a tightly capped cup of coffee.
Isolated system: Neither mass nor energy can cross the selected boundary i.e. neither mass
nor energy can transfer between the system and surroundings. Ex. (approximate): coffee in a
closed, well-insulated thermos bottle.
Properties of a system
In thermodynamics a property is ‘any characteristic of a system that is associated with the
energy and can be quantitatively evaluated’ i.e. any characteristic of a System is known as its
PROPERTY. Eg. Pressure (P), Volume (V), Temperature (T) and mass (m), Viscosity (μ), Electric
Resistance (R), Thermal Conductivity (k), etc.
Extensive Dependent on mass of system ie. varies directly with the mass
- mass, volume, energy, enthalpy
Intensive : Independent on mass of system.

Eg. Temperature, Pressure, and Density
Specific Extensive properties per unit mass.

- e.g. Sp. Vol (v=V/m), Sp. Enthalpy (h=H/m), etc.

State function
Some values of system properties have nothing to do with

the history of the system, they are decided by system state.
The change values depend on the initial and the final
state, and have nothing to do with the change ways. 3
This kind of physical quantity is called state function.
State function is defined as “a property of thermodynamic

system which has a definite value for a particular state of the
system”.
It is independent of the manner in which the state is reached. It is depended on only initial
and final state of the system but not on the path.
Ex. Pressure, temperature, volume and energy.
Equilibrium
Equilibrium : State of Balance
Thermal Equilibrium :
- NO Temperature Gradient throughout the system.
Mechanical Equilibrium :
- NO Pressure Gradient throughout the system.
Phase Equilibrium :
- System having more than 1 phase.
- Mass of each phase is in equilibrium.
Chemical Equilibrium :
- Chemical composition is constant
- NO reaction occurs.
Process
Process: Any change a system undergoes from one

equilibrium state to another is known as PROCESS.
Series of states through which system passes during the

process is known as its PATH.

Process proceeds in such a manner that system remains infinitesimally close to equilibrium
conditions at all times. It is known as QUASI-STATIC or QUASI-EQUILIBRIUM Process.
If the path is not infinitesimally close to equilibrium conditions

at all times, the process is called non quasi-static process.
4
Quasi-Static Process is denoted by a continuous line and
Non-Quasi-Static Process is denoted by a dashed line.
Types of Thermodynamic Processes
Any of the state function or perticular property remains

constant through out the process, the prefix iso- is often used
to designate that perticular process. Ex. Iso-baric process, Iso-
thermal, iso-choric etc..
Isobaric process: A process during which the pressure P

remains constant (ΔP = 0).
Isochoric (or isometric) process: A process during which the

volume V remains constant (ΔV=0).
Isothermal process: A process during which the temperature

T remains constant(ΔT=0).
Isenthalpic process: A process during which the enthalpy H

remains constant(ΔH=0)
Isentropic process: A process during which the entropy S

remains constant(ΔS=0)
Reversible Process: Process that can be reversed without leaving any trace on the
Surroundings. I.e. Both, System and Surroundings are returned to their initial states at the
end of the Process. This is only possible when net Heat and net Work Exchange between the
system and the surroundings is ZERO for the Process.
Irreversible Process: Most of the Processes in nature are irreversible i.e. having taken place,
they cannot reverse themselves spontaneously and restore the System to its original state.
Ex. Hot cup of coffee cools down when exposed to Surroundings But not Warm up by gaining
heat from Surroundings i.e. w/o external heat supply.
Adiabatic process: A process that has no heat transfer into or out of the system. It can be
considered to be perfectly insulated.

Temperature
Temperature is a measure of how much kinetic energy the particles of a system have.
- No exact definition.
- Broad definition : “degree of hotness or coldness” 5
- This definition is based on our physiological sensation.
- Hence, may be misleading. E.g. Metallic chair may feel cold than wooden chair; even
at same temperature.
- Properties of materials change with temperature.
- We can make use of this phenomenon to deduce exact level of temperature.
Temperature Scales
1. Celsius Scale ( ºC ) – SI System

2. Fahrenheit Scale ( ºF ) – English System
3. Kelvin Scale ( K ) – SI System
4. Rankine Scale ( R ) – English System
Thermodynamic Temperature Scale – Kelvin scale
Pressure
Definition: Normal Force exerted by a fluid per unit Area.
SI Units:
1 Pa = 1 N/m2
1 kPa = 103 Pa
1 MPa = 106 Pa = 103 kPa
1 bar = 105 Pa = 0.1 MPa = 100 kPa
1 atm = 101325 Pa = 101.325 kPa = 1.01325 bar
1 kgf/cm = 9.81 X 104 N/m2 = 0.981 bar = 0.9679 atm
2
Absolute Pressure: Actual Pressure at a given position. It measured relative to absolute

vacuum i.e. absolute zero pressure.
Gauge Pressure: Pressure more

than local atmospheric pressure
is known as Gauge Pressure. I.e.
P (gauge) = P (abs) – P (atm)
Vacuum Pressure: Pressure less

than local atmospheric pressure
is known as Vacuum Pressure. I.e.
P (vacuum) = P (atm) – P (abs)

Zeroth Law of Thermodynamics
“If two bodies are in thermal equilibrium with a third body, there are also in thermal
equilibrium with each other.”
If object A is in thermal equilibrium with object B, and object B is separately in thermal 6

equilibrium with object C, then objects A and C will be in thermal equilibrium if they are placed
in thermal contact.
Ex. Hot cup of tea or coffee, cool drink

when exposed to the atmosphere for
some time the temperature of coffee and
cool drink will be same due to thermal
equilibrium. I.e. when a body is brought
in contact with another body at different
temperature, heat is transferred from the body at higher temperature to that with lower one;
till both attain a thermal equilibrium.
Work (w)
Physically, work is performed on an object when the object moves some distance due to the
application of a force F.
Mathematically, it is the dot product of the force vector F and the distance vector s
work = F.s = │F││s│cos θ ------- (2.1) where θ is the angle between the vectors.
Work has units of joules, like energy.
Work is a way to transfer energy. Energy is defined as the ability to do work, so it makes sense
that energy and work are described using the same units.
In c.g.s system, the unit of energy is erg. Which is defined as the work done when a resistance
of one dyne is moved through a distance of 1cm. Joule (J) is SI unit of energy.
1 J = 107 ergs.
James Joule, 1980 showed that W 𝛼 H or w = JH -------(2.2)
Where w is work done; H is heat produced; J is Joule mechanical equivalent of heat.
Here J = 4.184 X 107 ergs = 4.184 J =1 calorie.
Energy manifests itself as mechanical work as per joule’s and also as heat energy, electrical
energy and chemical energy. What ever the form of energy , energy is composed of two

factors (i) an intensity factor and (ii) a capacity factor. The product of these factors gives the
energy.
Heat energy = temperature (Intensity factor) X heat capacity (capacity factor)

If the ‘m’ kg of substance and specific heat (s) heated through (t),
Heat energy = m.s.t kJ 7
When a current flows in in an electric circuit for a given interval of time,

Electrical energy = potential difference V (Intensity factor). C.t (capacity factor)
=V (volts).Q (coulombs) = V.Q Joules
When ‘m’ kg mass of moved through a height of ‘h’ m,

the work done against gravity = mg (intensity factor) · h (capacity factor) Joules
w = mgh --------2.3
Problem 1: To raise a book (of mass about 1.0 kg) from the floor to the table 75 cm above.
−2
Required Work = (1.0kg) × (9.81 m s ) × (0.75 m)
= 7.4 kg m2 S-2 = 7.4 J we knew that 1 J = 1 kg m2 S-2
The most common form of work studied by basic thermodynamics involves the changing volume of a
system. Consider Figure. (a) A frictionless piston confines a sample of a gas in an initial volume Vi, with
an initial pressure pi. Initially, what keeps the piston at a fixed position is the external pressure of the
surroundings, pext.
If the piston moves out, Figure (b), then the system is doing work on the surroundings. The
infinitesimal amount of work dw lost by the system to the surroundings for an infinitesimal change in
volume dV while acting against a constant external pressure pext is defined as
dw = -pext dV ----------------- (2.4)
The negative sign indicates that the work done contributes to a decrease in the amount of energy of
the system. Equation 2.4 can be rewritten as
𝐅𝐨𝐫𝐜𝐞
work = 𝒂𝒓𝒆𝒂
X volume = force x distance = F. s which is equation 2.1.
If the piston moves inward, Figure (c), then the surroundings are doing work on the system, and the
amount of energy in the system is increased.
w = -∫ 𝐩𝐞𝐱𝐭 𝐝𝐕 ---------- (2.5)
If pext is the constant throughout the process,
𝐕𝐟
w = - 𝐩𝐞𝐱𝐭 ∫ 𝐝𝐕 = - 𝐩𝐞𝐱𝐭 ∫𝐕𝐢 𝐕 = - 𝐩𝐞𝐱𝐭 (Vi-Vf) = - 𝐩𝐞𝐱𝐭 𝚫𝐕 ---------- (2.6)

Self-test 1: Calculate the work done by a system in which a reaction results in the formation
of 1.0 mol CO2 (g) at 25°C and 100 kPa. Hint. The increase in volume will be 25 dm3 under
these conditions if the gas is treated as perfect; use the relations 1 dm3 = 10−3 m3 and 1 Pa
m3 = 1 J. [Answer: 2.5 kJ]
8
By using pressures in units of atm and volumes in units of L, we get a unit of work in L●atm.
This is not a common work unit. The SI unit for work is the 𝑷𝑽
joule, J. Universal gas constant R =
𝒏𝑻
Based on STP values, R value
However, using the various values of R, it can be shown that can be calculated
R = 8.314 Pa m3 K-1 mol-1
1 L● atm = 101.325 J.
R = 8.314 kPa L K-1 mol-1
This conversion factor is very useful to get work into its proper R = 8.314 X 10-2 bar L K-1 mol-1
SI units.
R = 8.314 J K-1 mol-1
If volume were expressed in units of m3 and pressure in Pascal, R = 0.082058 L atm K-1 mol-1
units of joules would be obtained directly because
R = 1.987 cal K-1 mol-1
N
Pa X m3 = m2 X m3 = N X m = J R = 62.36 torr K-1 mol-1
Problem 2. Consider an ideal gas in a piston chamber, where the initial volume is 2.00 L
and the initial pressure is 8.00 atm. Assume that the piston is moving up (that is, the system
is expanding) to a final volume of 5.50 L against a constant external pressure of 1.75 atm.
Also assume constant temperature for the process.
a. Calculate the work for the process. b. Calculate the final pressure of the gas.
Sol:
a. First, the change in volume is needed. We find it as follows:
ΔV = Vf - Vi = 5.50 L - 2.00 L=3.50 L
To calculate the work against the constant external pressure, we use equation 2.5:
w = - Pext ΔV = -(1.75 atm)(3.50 L) = -6.13 L atm
If we want to convert units to the SI units of joules, we use the appropriate conversion factor:
101.325J
w = -6.13 L· atm 1L . atm = -621 J
That is, 621 joules have been lost by the system during the expansion.

b. Because of the assumption of an ideal gas, as per Boyle’s law PiVi = PfVf We get
(2.00 L)(8.00 atm) = (5.50 L)(Pf) Pf = 2.91 atm
Work done on free expansion

9
Figure illustrates a condition that occasionally occurs with gases: the
expansion of a gas into a larger volume, which is initially a vacuum.
In such a case, because the gas is expanding against a pext of 0, by
the definition of work in equation 2.4 the work done by the gas
equals zero. Such a process is called a free expansion
work = 0 for free expansion
Problem 3: From the conditions and the given definitions of the system, determine
whether there is work done by the system, work done on the system, or no work done.
a. A balloon expands as a small piece of dry ice (solid CO2) inside the balloon sublimes (balloon
= system).
b. The space shuttle’s cargo bay doors are opened to space, releasing a little bit of residual
atmosphere (cargo bay = system).
c. Gaseous CHF2Cl, a refrigerant, is compressed in the compressor of an air conditioner, to

liquefy it (CHF2Cl = system).
Sol:
a. Because the balloon is increasing in volume, it is undoubtedly doing work: Work is done by
the system.
b. When the shuttle’s cargo bay doors are opened in space, the bay is being opened to
vacuum (although not a perfect one), so we are considering relatively free expansion.
Therefore, no work is done.
c. When CHF2Cl is compressed, its volume is decreased, so work is being done on the system.
Reversible, isothermal expansion work
Reversible or irreversible processes can be explained based on volume changes, temperature

changes and also pressure changes. Gaseous systems are useful examples for thermodynamics
especially so for reversible changes because most reversible changes occur by letting the
external pressure equal the internal pressure.
Pext = Pint for reversible change.

The following substitution can then be made for reversible changes
wrev =-∫ Pint dV ------(2.7)
𝒏𝑹𝑻
By substituting Pint as per ideal gas equation we get wrev = − ∫ dV
10
𝑽
If T remains constant, n, R and T can be taken outside from the integral sign.
𝟏
wrev = −𝒏𝑹𝑻 ∫ 𝑽dV
𝑽𝒇
wrev = -nRT ln 𝑽| 𝑽
𝒊
wrev = -nRT (ln Vf – ln Vi )
𝑽
wrev = -nRT ln 𝑽𝒇 ------- (2.8)
𝒊
As per Boyle’s law Equation. 2.8 can be rewrite as
𝑷
Wrev = -nRT ln 𝑷 𝒊 ------ (2.9) for an ideal gas undergoing an isothermal process.
𝒇
Problem 4: Gas in a piston chamber kept in a constant-temperature bath at 25.0°C expands

from 25.0 mL to 75.0 mL very, very slowly. If there is 0.00100 mole of ideal gas in the
chamber, calculate the work done by the system.
Sol:
Given data
n = 0.001 mole
-1 -1
R = 8.314 J mole K
0
t = 25 C; T = 25 +273.15 =398.15 K
Vf = 75.0 mL
Vi = 25.0 mL
𝑉
We knew that w = - nRT (ln 𝑉𝑓 ) for reversible processes
𝑖
-1 -1 75 𝑚𝐿
Therefore w = - (0.001 mol ● 8.314 J mol K ● 298.15 K (ln ) = -2.7232 J
25𝑚𝐿
Heat (q)
Heat is denoted by q. It is more difficult to define than work.
Around 1780 Benjamin Thompson, later Count Rumford, kept track and concluded that the
amount of heat was related to the amount of work done in the process.
In the 1840s, careful experiments by the English physicist James Prescott Joule verified this.

- Work and heat were manifestations of the same thing.

- The phrase “mechanical equivalent of heat” is still used occasionally and emphasizes
their relationship.
- The SI unit of energy and work and heat, the joule, is named in Joule’s honour
- Heat is obtained from mechanical work, similarly work is obtained from heat.
11
Heat may be defined as ‘energy in transit from a high temperature object to a lower
temperature object’. The appropriate term for the microscopic energy in an object is internal
energy. The internal energy may be increased by transferring energy to the object from a
higher temperature (hotter) object - this is properly called heating.
Heat is measured in calories or Joules. 1 calorie = 4.18 Joules
Calorie: The heat required to raise the temperature of 1g of water by 10C from 150C to 160C.
Heat transfer
Walls that permit heating as a mode of transfer of energy are called diathermic. Ex. A metal
container. Walls that do not permit heating even though there is a difference in temperature
are called adiabatic. Ex. The double walls of a vacuum flask.
Energy Transfer in from of Heat by 3 ways:
Conduction: Transfer of Energy from a more energetic particle of a substance to the adjacent
less energetic one, as a result of interaction between them.
Convection: Transfer of Energy between a solid surface and the adjacent fluid that is in motion.
It involved both, the combined effect of conduction and fluid motion.
Radiation: Transfer of Energy due to the emission of electromagnetic waves.
Measurement of heat
If heat is entering the system and ‘q’ is positive, that process is described as endothermic. If
heat is leaving the system and ‘q’ is negative, that process is called exothermic.
The amount of heat necessary to change the temperature is proportional to the magnitude of
the temperature change, ΔT and the mass of the system m:
q α m· ΔT
q = m · c· ΔT --------- (2.10)
where ‘c’ is specific heat or specific heat capacity, also shown some times as ‘s’
q = C·ΔT (since C = heat capacity = m. c) --------- (2.11)
Problem 5: If the heat capacity of a beaker of water is 0.50 kJ K-1 , and we observe a
temperature rise of 4.0 K, then we can infer that the heat transferred to the water is..
As per the data C = 0.50 kJ K-1: ΔT = 4.0 K
We knew that q = C · ΔT
Therefore q = (0.50 kJ K-1) × (4.0 K) = 2.0 kJ

Problem 6:
a. Assuming that 400. J of energy is put into 7.50 g of iron, what will be the change
in temperature? Use c = 0.450 J/g. K
b. If the initial temperature of the iron is 65.0°C, what is the final temperature?
Sol:
a. Given data 12
Heat q = 400 J
mass m = 7.50 g
c = 0.450 J·g-1·K-1
we knew that q = m ·c·ΔT
therefore +400. J = (7.50 g)(0.450 J·g-1·K-1) ΔT
+400. J
ΔT = (7.50 g)(0.450 J·g-1·K-1)
ΔT = +118K
The temperature increases by 118 K, which is equal to a temperature change of 118°C.
b. With an initial temperature of 65.0°C, an increase of 118°C brings the sample to 183°C.
Problem 7: Assume that a 40.0-kg weight (which experiences a force due to gravity of 392
newtons) falls a distance of 2.00 meters. The paddles immersed in the water transfer the
decrease in potential energy to the water, which heats up. Assuming a mass of 25.0 kg of
water in the vat, what is the expected temperature change of the water? The specific heat
of water is 4.18 J·g-1 K-1
Sol:
Work done on the water is taken as heat produced in the water,
As per given data
F = 392 newtons
S = 2.00 meters
Work w = F·s
w = (392 N) (2.00 m)
w = 784 N . m
w = 784 J which is equal to heat ‘q’
There fore, q = 784 J
m = 25.0 kg = 25000 g
c = 4.18 J·g-1·K-1K
We knew that q = m ·c·ΔT
𝑞 784 J
ΔT = 𝑚 𝑐 = 25000 g ● 4.18 J·g-1·K-1 = 0.00750
Heat influx during expansion
In certain cases, we can relate the value of q to the change in volume of a system, and so can
calculate, for instance, the flow of energy as heat into the system when a gas expands.
For the isothermal expansion of a perfect gas: q = −w

For the isothermal, reversible expansion of a perfect gas:
Vf
Wrev = -nRT ln Vi
Vf
Therefore q = nRT ln Vi
13
We interpret this expression as follows:
 When Vf >Vi, as in an expansion, the logarithm is positive and we conclude that q > 0,
as expected: flows as heat into the system to make up for the energy lost as work.
 The greater the ratio of the final and initial volumes, the greater the influx of energy as
heat.
 The higher the temperature, the greater the quantity of heat that must enter for a given
change in volume: we have seen that more work is done at a higher temperature, so
more heat must enter to make up for the energy lost.
Heat capacity (C) and specific heat capacity (c)
First, we note that the heat capacity is an extensive property.

It is more convenient to report the heat capacity of a substance as an intensive property.
We therefore use either the Specific heat (or) specific heat capacity, Cs, (Cs = C/m, J K−1 g−1)
or Molar heat capacity, Cm, (Cm = C/n, J K−1 mol−1).
To obtain the heat capacity of a sample of known mass or that contains a known amount of
substance, we use these definitions in the form
C = m Cs or C = n Cm, respectively.
Heat capacity at constant pressure, Cp. Heat capacity at constant volume CV, and their
respective molar values are denoted as CP, m and CV, m.
First law of thermodynamics
“Energy can neither be created nor destroyed although it can be transform from one form to
another in a process”.
 Also called as law of conservation of energy
 States that it is impossible to construct a perpetual motion machine (a machine can
produce energy without expenditure of energy which operating in cycles).
Internal energy E or U
Energy possessed by a system due to vibrational, translational and rotational motions of the
molecules plus the energy of the electrons and nuclei is called internal energy.
Value is fixed and depends on temperature, pressure, volume, chemical nature and
composition. Internal energy is an extensive property while the molar internal energy is an
intensive property.
It is expressed in Joules or ergs. 1J = 107 ergs.
Actual value of internal energy cannot be determined but, change in internal energy
(ΔE or ΔU) accompanying a chemical or physical process is measurable.
ΔU = UB – UA ----------(2.12)
In isothermal process ΔU = 0

In all investigations of energy changes in systems, it has been found that when the total energy
of a system changes, the energy change goes into either work or heat, nothing else.
Mathematically, this is written as
ΔU = q + w ----------(2.13)
If work is done by the surroundings on the system (compression of gas), w is positive so that,
ΔU = q + w 14
If, however, work is done by the system on the surroundings (expansion of gas), w is negative
so that, ΔU = q – w
If a system is insulated well enough, heat will not be able to get into the system or leave the
system. In this situation, q = 0. Such systems are called adiabatic.
For adiabatic processes, ΔU = w
Illustration Problem 8: The molar heat capacity of water at constant pressure, Cp,m is 75 J K-1
mol-1. Suppose a 1.0 kW kettle (where 1 W = 1 J s-1) is turned on for 100 s. The energy
supplied in that interval (the product of the power and the time) is q and
It follows that the increase in temperature of 1.0 kg of water (55.5 mol H O, from n = m/M)
2
in the kettle is approximately
q = (1.0 kW) × (100 s) = (1.0 × 103 J s-1) × (100 s) = 1.0 × 105 J
It follows that the increase in temperature of 1.0 kg of water (55.5 mol H O, from n = m/M)
2
in the kettle is approximately
q q 1.0 x 105 J
ΔT = 𝐶 = = 75J = +24 K
𝑝 n Cpm (55.5 mol) x ( )
K mol
Problem 9. Suppose one person 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.
Solution
From the given data
w = −622 kJ
q = −82 kJ
ΔU = ?
ΔU = w + q = (−622 kJ) + (−82 kJ) = −704 kJ
We see that the person’s internal energy falls by 704 kJ.
Problem 10. A sample of gas changes in volume from 4.00 L to 6.00 L against an external
pressure of 1.50 atm, and simultaneously absorbs 1000 J of heat. What is the change in the
internal energy of the system?
Solution
From the given data
q = +1000 J; Vi = 4.00 L; Vf = 6.00 L; Pext = 1.50 atm
ΔU = ?
w = -Pext ΔV
w = - (1.50 atm)(6.00 L - 4.00 L) = -(1.50 atm)(2.00 L) = 3.00 L· atm = 3x101.325 J · L-1 · atm-1
w = -304 J
The change in internal energy is the sum of w and q;
Therefore ΔU=q+w = 1000 J + (-304 J) = + 696 J

Self-test 2: An electric battery is charged by supplying 250 kJ of energy to it as electrical

work (by driving an electric current through it), but in the process it loses 25 kJ of energy as
heat to the surroundings. What is the change in internal energy of the battery?
Answer: +225 kJ
Problem 11. Calculate w and for the conversion of one mole of water at 100 0C to steam at
1 atm pressure. Heat of vaporisation of water at 1000C is 40670 J mol-1. 15
Solution
From the given data
q = heat of vaporisation = +40670 J.
P = 1 atm = 101325 N/m-2
Vi = 1 mole water = 18 g = 18 mL = 18x10-6 m3
Vf = 1 mole of steam at 1000C
𝑇𝑓 𝑉𝑖 0.0224 m3x 373.15 K
Vf = = = 0.306 m3
𝑇𝑖 273.15 K
ΔU = ?
w = -Pext ΔV
w = - (101325 N m-2) (0.0306 m3 - 18x10-6 m3)
w = -3100 J
The change in internal energy is the sum of w and q;
ΔU=q+w
= (+40670 J)+(-3100 J)
Δ U= +37570 J
State function
A state function is any thermodynamic property whose value for the process is independent of
the path. It depends only on the state of the system (in terms of state variables like P, V, T, n),
not on its history or how the system got to that state.
A thermodynamic property whose value for the process does depend on the path is not a state
function.
State functions are symbolized by capital letters; non-state functions are symbolized by
lowercase letters.
Internal energy is a state function. Work and heat are not.
Internal energy as state function
For an infinitesimal change in a system, the infinitesimal changes in the work, heat, and internal
energy are represented as dw, dq, and dU. For a complete process, these infinitesimals are
integrated from initial to final conditions.
∫ 𝑑𝑤 = 𝑤
∫ 𝑑𝑞 = 𝑞

But ∫ 𝑑𝑈 = 𝛥𝑈
The differentials dw and dq are called inexact differentials, meaning that their integrated values
w and q are path-dependent. By contrast, dU is an exact differential, meaning that its
integrated value ΔU is path-independent.
16
In another way ΔU= Uf -Ui but w ≠ wf - wi and q ≠ qf – qi
For an infinitesimal change in a system,
dU = dq + dw which is the infinitesimal form of the first law.
But when we integrate this equation, we get
ΔU = q + w -------- (2.13)
If no work is performed during the course of a process, then dU = dq and ΔU = q.

The relationship with heat under these conditions is sometimes written as
dU = dqV ------ (2.14)
ΔU = qV ------ (2.15)
At constant volume, q may be replaced by the change in internal energy of the substance ΔU,
q ΔU
so the heat capacity CV = ΔT can be write as CV = ΔT ------- (2.16)
By considering, an infinitesimal change in temperature, dT, and the accompanying infinitesimal
change in internal energy, dU, Eqn. 2.16 can be written as
dU
CV = dT ------- (2.17)
At constant volume, we attach a subscript V to the derivative, and write as
𝜕𝑈
CV = ( 𝜕𝑇 )V ------ (2.18)
Problem 12: A 1.00-L sample of gas at 1.00 atm pressure and 298 K expands isothermally
and reversibly to 10.0 L. It is then heated to 500 K, compressed to 1.00 L, and then cooled
to 25°C. What is DU for the overall process?
Solution
ΔU = 0 for the overall process. Remember that a state function is a variable whose value
depends on the instantaneous conditions of the system. Because the initial and final
conditions of the system are the same, the system has the same absolute value of internal
energy (whatever it might be), so that the overall change in the internal energy is zero.
Enthalpy or Heat content (H)
“The energy stored with in the substance or the system that is available for conversion into
heat is called enthalpy or heat content of the substance or the system”. It is denoted by ‘H’.

Suppose a state of system changes in volume from Vi to Vf at constant pressure P,
Then the work done w = -P (Vf – Vi)
By substituting this in eq. ΔU = q + w ( Eq.2.13)

17
we get ΔU = q – P (Vf – Vi)
Uf – Ui = q – PVf + PVi ------ (2.19)
(Uf + PVf) – (Ui+ PVi) = q ------ (2.20)
The quantity U + PV is known as the enthalpy of the system.
Thus H = U + PV ------ (2.21)
The pressure in equation 2.21 is the pressure of the system, Pint.
As the U, P & V are definite properties, H is also definite property.
From the eq. 2.20, we get HB – HA = q at constant pressure
ΔH = q or ΔH =qP ------ (2.22)
From the eq. 2.19, we can also write as
(Uf - Ui) + (PVf - PVi) = q ------ (2.23)
By substituting the value of ‘q’ (eq. 2.23) in eq. 2.22,
We get ΔH = (Uf - Ui) + (PVf - PVi)
ΔH = ΔU + P(Vf - Vi)
ΔH = ΔU + P ΔV ------ (2.24)
Enthalpy is an extensive property and the molar enthalpy, Hm = H/n, of a substance, is an

intensive property,
V
Let the molar internal energy is Um and the molar volume,Vm = n, of the substance at constant
pressure, Eq. 2.21 can be write as
Hm = Um + PVm ------ (2.25)
This relation is valid for all substances.
V
For a perfect ideal gas we knew that PV = nRT or P(n)= RT or PVm = RT

and obtain for a perfect gas: Hm = Um + RT ------ (2.26)
or ΔH = ΔU + Δng RT ------ (2.27)
Derivation for Heat transfers at constant pressure

18
Consider a system open to the atmosphere, so that its pressure p is constant and equal to the
external pressure Pex.
Equation 2.24(ΔH = ΔU + PΔV) can write as
ΔH = ΔU + Pex ΔV -------- (2.28)
However, we know that the change in internal energy (eq. 2.13) is
ΔU = q + w or ΔU = q + − Pex ΔV (since w = − Pex ΔV).
When we substitute that expression into this one we obtain
ΔH = (− Pex ΔV + q) + Pex ΔV
ΔH = q which is Eq. 2.22.
Note: The result expressed by Eq. 2.22(ΔH = q), that at constant pressure, with no non-
expansion work, we can identify the energy transferred by heating with a change in enthalpy
of the system, is enormously powerful. It relates a quantity of the energy transferred as heat
at constant pressure to the change in the enthalpy.
Problem 13. The heat of formation of methane at constant pressure at 250C is -74.85kJ mol-1.
What will be the heat of formation at constant volume?
Solution:
C(s) + 2 H2(g) CH4(g) H = -74.85kJ/mol
T = 250C + 273.15 = 298.15K
Δng = 1-2 =-1mol
R = 8.314 J mol-1 K-1
ΔH = - 74.85 kJ/mol
ΔH = ΔU + Δng RT
ΔU= ΔH - Δng RT
ΔU= -74.85 kJ/mol – (-1 x 8.314 J mol-1 K-1 x 298.15K)
ΔU= -72.37kJ/mol

The temperature variation of enthalpy
We have seen that the internal energy of a

system rises as the temperature is increased.
Enthalpy also rises when the temperature is 19

increased.
Just as we saw that the constant-volume heat

capacity tells us about the temperature
dependence of the internal energy at constant
volume, so the constant-pressure heat
capacity tells us how the enthalpy of a system
changes as its temperature is raised at
constant pressure.
We knew that C = q/ΔT(eq. 2.22) ; at constant pressure, ΔH = q (eq. 2.22)
𝛥𝐻
∴ heat capacity at constant pressure CP = 𝛥𝑇 ------(2.29)
Problem 14: When the temperature of 100 g of liquid water (5.55 mol H2O) is raised from
20°C to 80°C (so ΔT = +60 K) at constant pressure, calculate the change in enthalpy of the
sample. (The molar heat capacity of water as liquid is 75.29 J K-1mol-1)
Sol:
ΔH = Cp ΔT = n Cp,m ΔT
= (5.55 mol) × (75.29 J K-1 mol-1) × (60 K) = +25 kJ
The heat capacity at constant pressure is

the slope of the curve showing how the
enthalpy varies with temperature;
The heat capacity at constant volume is

the corresponding slope of the internal
energy curve.
Note that the heat capacity varies with

temperature (in general), and that Cp is
greater than CV.
b c
Cp m = a + + 2
, T T ------ (2.30)
with values of the constants a, b, and c obtained by fitting this expression to experimental data.
At very low temperatures, non-metallic solids are found to have heat capacities that are
proportional to T3 Cp,m = aT3 where ‘a’ is another constant

20
Fig. shows the variation of heat capacity with temperature as expressed by the empirical
formula in eq. 2.17a. For this plot we have used the values for carbon dioxide and nitrogen:
The circles show the measured values at 298 K.
Relation between CP and CV:
Because we know that the difference
between the enthalpy and internal energy of a
perfect gas depends in a very simple way on the
temperature (eq. 2.26),
We can suspect that there is a simple relation
between the heat capacities at constant volume
and constant pressure.
Hm = Um + RT
Hm - Um = RT
When the temperature increases by ΔT, the
molar enthalpy increases by ΔHm and the molar internal energy increases by ΔUm, so
ΔHm − ΔUm = R ΔT
Now divide both sides by ΔT, which gives
Δ𝐻𝑚 Δ𝑈𝑚
− =𝑅
Δ𝑇 Δ𝑇
CP,m – CV,m = R
Δ𝐻𝑚 ΔU𝑚
(Since CP = ; CV = )
Δ𝑇 Δ𝑇

1. Calculate the work done by a gas when it expands through (a) 1.0 cm3, (b) 1.0 dm3
against an atmospheric pressure of 100 kPa. What work must be done to compress
the gas back to its original state in each case?
2. Calculate the work done by 2.0 mol of a gas when it expands reversibly and
isothermally from 1.0 dm3 to 3.0 dm3 at 300 K.
3. A sample of methane of mass 4.50 g occupies 12.7 dm3 at 310 K. (a) Calculate the work 21
done when the gas expands isothermally against a constant external pressure of 30.0
kPa until its volume has increased by 3.3 dm3. (b) Calculate the work that would be
done if the same expansion occurred isothermally and reversibly.
4. In the isothermal reversible compression of 52.0 mmol of a perfect gas at 260 K, the
volume of the gas is reduced from 300 cm3 to 100 cm3. Calculate w for this process.
5. A sample of blood plasma occupies 0.550 dm3 at 0°C and 1.03 bar, and is compressed
isothermally by 0.57 per cent by being subjected to a constant external pressure of
95.2 bar. Calculate w.
6. A strip of magnesium metal of mass 12.5 g is dropped into a beaker of dilute
hydrochloric acid. Given that the magnesium is the limiting reactant, calculate the
work done by the system as a result of the reaction. The atmospheric pressure is 1.00
atm and the temperature is 20.2°C.
7. Calculate the work of expansion accompanying the complete combustion of 10.0 g of
sucrose (C12H22O11) to carbon dioxide and (a) liquid water, (b) water vapour at 20°C
when the external pressure is 1.20 atm.
8. We are all familiar with the general principles of operation of an internal combustion
reaction: the combustion of fuel drives out the piston. It is possible to imagine engines
that use reactions other than combustions, and we need to assess the work they can
do. A chemical reaction takes place in a container of cross-sectional area 100 cm2; the
container has a piston at one end. As a result of the reaction, the piston is pushed out
through 10.0 cm against a constant external pressure of 100 kPa. Calculate the work
done by the system.
9. What is the heat capacity of a sample of liquid that rose in temperature by 5.23°C
when supplied with 124 J of energy as heat?
10. A cube of iron was heated to 70°C and transferred to a beaker containing 100 g of
water at 20°C. The final temperature of the water and the iron was 23°C. What is (a)
the heat capacity, (b) the specific heat capacity, and (c) the molar heat capacity of the
iron cube? Ignore heat losses from the assembly.
11. The high heat capacity of water is ecologically benign because it stabilizes the
temperatures of lakes and oceans: a large quantity of energy must be lost or gained
before there is a significant change in temperature. Conversely, it means that a lot of
heat must be supplied to achieve a large rise in temperature. The molar heat capacity
of water is 75.3 J K−1 mol−1. What energy is needed to heat 250 g of water (a cup of
coffee, for instance) through 40°C?
12. A current of 1.55 A from a 110 V source was passed through a heater for 8.5 min. The
heater was immersed in a water bath. What quantity of energy was transferred to the
water as heat?
13. When 229 J of energy is supplied as heat to 3.00 mol Ar(g), the temperature of the
sample increases by 2.55 K. Calculate the molar heat capacities at constant volume
and constant pressure of the gas.

14. The heat capacity of air is much smaller than that of water, and relatively modest
amounts of heat are needed to change its temperature. This is one of the reasons why
desert regions, though very hot during the day, are bitterly cold at night. The heat
capacity of air at room temperature and pressure is approximately 21 J K−1 mol−1. How
much energy is required to raise the temperature of a room of dimensions 5.5 m × 6.5
m × 3.0 m by 10°C? If losses are neglected, how long will it take a heater rated at 1.5 22
kW to achieve that increase given that 1 W = 1 J s−1?
15. The transfer of energy from one region of the atmosphere to another is of great
importance in meteorology for it affects the weather. Calculate the heat needed to be
supplied to a parcel of air containing 1.00 mol air molecules to maintain its
temperature at 300 K when it expands reversibly and isothermally from 22 dm3 to 30.0
dm3 as it ascends.
16. The temperature of a block of iron (CV,m = 25.1 J K−1 mol−1) of mass 1.4 kg fell by 65°C
as it cooled to room temperature. What is its change in internal energy?
17. In an experiment to determine the calorific value of a food, a sample of the food was
burned in an oxygen atmosphere and the temperature rose by 2.89°C. When a current
of 1.27 A from a 12.5 V source flowed through the same calorimeter for 157 s, the
temperature rose by 3.88°C. What energy is released as heat by the combustion?
18. A laboratory animal exercised on a treadmill that, through pulleys, raised a 250 g mass
through 1.85 m. At the same time, the animal lost 10.0 J of energy as heat. Disregarding
all other losses, and regarding the animal as a closed system, what is its change in
internal energy?
19. In preparation for a study of the metabolism of an organism, a small, sealed
calorimeter was prepared. In the initial phase of the experiment, a current of 22.22
mA from a 11.8 V source was passed for 162 s through a heater inside the calorimeter.
What is the change in internal energy of the calorimeter?
20. In a computer model of the atmosphere, 20 kJ of energy was transferred as heat to a
parcel of air of initial volume 1.0 m3. What is the change in enthalpy of the parcel of
air?
21. The internal energy of a perfect gas does not change when the gas undergoes
isothermal expansion. What is the change in enthalpy?
22. Carbon dioxide, although only a minor component of the atmosphere, plays an
important role in determining the weather and the composition and temperature of
the atmosphere. Calculate the difference between the molar enthalpy and the molar
internal energy of carbon dioxide regarded as a real gas at 298.15 K. For this calculation
treat carbon dioxide as a van der Waals gas and use the data in Table 1.5.
23. 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 DH and estimate the heat
capacity of the sample.
24. When 3.0 mol O2(g) is heated at a 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 29.4 J K−1 mol−1, calculate q, ΔH, and ΔU.
25. The molar heat capacity at constant pressure of carbon dioxide is 29.14 J K−1 mol−1.
What is the value of its molar heat capacity at constant volume?
26. Use the information in Exercise 2.25 to calculate the change in (a) molar enthalpy, (b)
molar internal energy when carbon dioxide is heated from 15°C (the temperature
when air is inhaled) to 37°C (blood temperature, the temperature in our lungs).

23

Question 1
Calculate the work done on the system when 1.00 mol of gas held behind a piston
expands irreversibly from a volume of 1.00 dm3 to a volume of 10.0 dm3 against an
external pressure of 1.00 bar. 24
You did not answer the question.
Correct answer:
b) -900 J
Feedback:
We know from eqn 2.1 that when a gas expand irreversibly, the work done on the system
is
The change in volume is
so that, remembering to convert the external pressure from bar to Pa, and the change in
volume from dm3 to m3
The value of the work done on the gas is negative because it loses energy.
Page reference: 51
Question 2
1.00 mol of gas in a cylinder is compressed reversibly by increasing the pressure from
1.00 bar to 10.0 bar at a constant temperature of 500 K. Calculate the work done on the
gas by the compression.
Correct answer:
a) +9570 J
Feedback:
When n mol of gas expands or contracts reversibly from a volume Vi to a volume Vf at
constant temperature T, the work done on the system is given by eqn 2.2
We know from Boyle's law that for a perfect gas at constant temperature
so that we can instead express the work done in terms of the pressures
Note that the work done on the system is positive. The system acquires energy as a result

of the compression.
Page reference: 53
Question 3
The temperature of a copper block of mass 423 g rises by 10.1°C. Calculate the heat 25
transferred, given that the specific heat capacity of copper is 385 J K-1 kg-1.
Correct answer:
b) 1.63 kJ
Feedback:
The heat absorbed by a system is related to the change in temperature by eqn 2.3b
where C is the heat capacity of the system. We can introduce the specific heat capacity,
so that, since a rise in temperature of 10.1°C is equivalent to a change of 10.1 K,
Page reference: 56
Question 4
Raising the temperature of 1.00 dm3 of water from a temperature of 25°C to 100°C at
constant pressure requires 312 kJ of heat. Calculate the molar heat capacity of water at
constant pressure.
Correct answer:
c) 75 J K-1 mol-1
Feedback:
We can modify eqn 2.3a so that it refers to the molar heat capacity Cm rather than just the
heat capacity
If we require the heat capacity at constant pressure, we must specify that the quantity of
heat transferred is also that at constant pressure. The molar mass of water is M = 18.02 g
mol-1. Thus, because 1.00 dm3 of water has a mass of 1.00 kg, it must correspond to an
amount
Hence

Page reference: 56
Question 5
A calorimeter was calibrated by passing an electrical current through a heater and 26

measuring the rise in temperature that resulted. When a current of 113 mA from a 24.1 V
source was passed through the heater for 254 s, the temperature of the calorimeter rose by
2.61 °C. Determine the heat capacity of the calorimeter.

Correct answer:
d) 265 J K-1
Feedback:
We know from eqn 2.4 that the heat that is transferred when a current flows through a
resistive device is
and, from eqn 2.4b, that the rise in temperature is given by
so that
Page reference: 57
Question 6
A perfect gas expands reversibly at a constant temperature of 298 K so that its volume
doubles. What is the change in the molar internal energy of the gas?

Correct answer:
b) 0 J mol-1
Feedback:
Although work is done when the gas expands, heat is also transferred. For an isothermal
expansion of a perfect gas, we can see from eqn 2.6 that the work done and the heat
transferred are equal and opposite
so that, from eqn 2.7, there is no change in the internal energy of the gas
Page reference: 59

Question 7
Which of the following statements is always true for a reaction in which there is no non-
expansion work?
You did not answer the question. 27

Correct answer:
b) ΔH = qp
Feedback:
Derivation 2.3 shows that if a reaction occurs at constant pressure so that we can write
then
Thus, for any reaction, we can interpret the enthalpy change as the heat that would be
transferred at constant pressure. Under adiabatic conditions, q = 0, and so ΔH = 0, but
under other conditions this is not always true.
In the same way, we can interpret the change in the internal energy as the heat that would
be transferred at constant volume
Page reference: 63
Question 8
Calculate the difference between the molar internal energy and the molar enthalpy for a
perfect gas at 298.15 K.

Correct answer:
c) 2.4790 kJ mol-1
Feedback:
Molar enthalpy is defined by eqn 2.12a
For a perfect gas, however,
so that
Thus
and the difference between the molar enthalpy and molar internal energy is

Page reference: 62
Question 9
For many substances, the variation with temperature of the molar heat capacity at 28
constant pressure of is given by the expression
For copper, a = 22.64 J K-1 mol-1, b = 6.28 × 10-3 J K-2 mol-1 with the value of c being
negligible. Estimate the change in the molar enthalpy of copper when it is heated from
293 to 323 K.
Correct answer:
b) +1.23 kJ mol-1
Feedback:
The molar heat capacity at constant pressure of a substance is defined in the brief
comment in section 2.10
To determine exactly the change in enthalpy on heating, it is necessary to integrate
but for functions of this type, we can instead make an estimate of the change by using eqn
2.18
where Ta,mean is the arithmetic mean ½(T1 + T2) and Tg,mean is the geometric mean (T1T2)½.
In this case, the calculation is simplified because c = 0, so that the approximation
becomes
Page reference: 64
Question 10
The molar heat capacity at constant volume of argon, Ar, is 12.47 J K mol-1. What is the
value of the molar heat capacity at constant pressure?
Correct answer:
d) 20.78 J K-1 mol-1
Feedback:
For a perfect gas, the relationship between the molar heat capacities at constant pressure
and constant volume are given by eqn 2.17

so that
29
Page | 29
Page reference: 65
Thermodynamics - Second Law

“The Second Law of Thermodynamics states that the state of entropy of the entire universe,
as a closed isolated system, will always increase over time. The second law also states that
the changes in the entropy in the universe can never be negative”.
“Whenever energy is transformed, there is a loss of energy through the release of heat.”
Although the mathematical and conceptual tools provided by the zeroth and first laws of
thermodynamics are very useful, we need more. There is a major question that these laws
cannot answer:
Will a given process occur spontaneously?
Nothing in the previous chapters addresses spontaneity, which is an important concept.
Thermodynamics helps to understand the spontaneity of processes—but only once we add
more of its tools. These tools are called the second and third laws of thermodynamics.
Natural and Reversible Processes
By the everyday observations suggest that changes
can be divided into two classes.
• A spontaneous change is a change that has a
tendency to occur without work having to be
done to bring it about.
• A spontaneous change has a natural tendency
to occur.
• A nonspontaneous change is a change that can
be brought about only by doing work.
• Nonspontaneous changes can be made to occur
by doing work
Ex. Compression of gas, heating of cooing object, etc..
Reversible and Irreversible Processes
A process i → f is irreversible if the system cannot be returned to the initial state i without
leaving a change in the surroundings. An irreversible process is also said to be spontaneous
or natural.

A process I → f is reversible if the system can be returned to the initial state i without leaving
any change in the surroundings.
Reversible Irreversible
Infinitesimal driving force Finite driving force
System traverses sequence of equilibrium 30
System traverses nonequilibrium states.
states. n
At any stage, an infinitesimal change in some
property can cause the process to reverse, and
the same sequence of states followed in
reverse.
No dissipative effects such as friction.
Limits of the First Law
Will a chemical or physical process occur spontaneously?
A process occurring inside a system is spontaneous if the surroundings are not rqeuired to
perform work on the system.
For example,
• If you drop a rock from a waist-high height, the rock will fall spontaneously, converting
its gravitational potential energy into heat.
• When the plunger of a spray can of hair spray is pressed, gas comes out spontaneously.
• When metallic sodium is placed in a jar filled with chlorine gas, a chemical reaction
occurs spontaneously, making sodium chloride as a product.
• Consider the isothermal, adiabatic free expansion of an ideal gas. The process is
spontaneous, but it occurs with no change in energy of the gas in the system.
These changes can be made to occur by performing some sort of work. For example, sodium
chloride can be melted and an electric current run through it, generating sodium and chlorine,
but in such a case we are forcing a nonspontaneous process to occur. The process is not
occurring on its own.
How can we predict which processes are spontaneous?
Consider the following process. NaCl(s) → Na+(aq) + Cl- (aq)
Which is the dissolution of sodium chloride in water. The change in enthalpy for this process
is an example of heat of solution, ΔsolnH. This particular process, which occurs spontaneously
(because sodium salts are soluble), has a ΔsolnH(25oC) of +3.88kJ/mol.
Entropy and the Second Law of Thermodynamics
In summary, we have identified two basic types of spontaneous physical process:

1. Matter tends to become disordered.

2. Energy tends to become disordered.
The measure of disorder used in thermodynamics is called the entropy, S.
When matter and energy become disordered, the entropy increases. That being so, we can 31
combine the two remarks above into a single statement known as the Second Law of
thermodynamics.
“The entropy of an isolated system tends to increase”.
“state of entropy of the entire universe, as a closed isolated system, will always
increase over time”.
“The second law also states that the changes in the entropy in the universe can
never be negative”.
“There is an increase in the sum of the entropies of the participating systems”.
“Whenever energy is transformed, there is a loss of energy through the release

of heat.”
Change in entropy for a system maintained at constant temperature

ΔS = qrev/T ------ (1)
That is, the change in entropy of a substance is equal to the energy transferred as heat to it
reversibly divided by the temperature at which the transfer takes place.
 The units of entropy are joules per kelvin (J K−1).
 Entropy is an extensive property. When we deal with molar entropy, an intensive property,
the units will be joules per kelvin per mole (J K−1 mol−1).
 The entropy is a state function, The entropy is a measure of the current state of disorder
of the system, and how that disorder was achieved is not relevant to its current value.
We need to understand about the definition in above eqn. the significance of the
term ‘reversible’,
Why heat (not work) appears in the numerator, and why temperature appears in
the denominator.
Why reversible?
• Reversible transfer of heat is smooth, careful, restrained transfer between two bodies
at the same temperature.
• By making the transfer reversible we ensure that there are no hot spots generated in
the object that later disperse spontaneously and hence add to the entropy.

Why heat and not work in the numerator?

• Transfer energy as heat we make use of the disorderly motion of molecules, whereas
to transfer energy as work we make use of orderly motion.
• It should be plausible that the change in entropy—the change in the degree of
disorder—is proportional to the energy transfer that takes place by making use of 32
disorderly motion rather than orderly motion.
Why temperature in the denominator?
• The presence of the temperature in the denominator takes into account the disorder
that is already present.
• If a given quantity of energy is transferred as heat to a hot object (one in which the
atoms have a lot of disorderly thermal motion), then the additional disorder generated
is less significant than if the same quantity of energy is transferred as heat to a cold
object in which the atoms have less thermal motion.
• The difference is like sneezing in a busy street (an environment analogous to a high
temperature) and sneezing in a quiet library (an environment analogous to a low
temperature)
Prob. 1: Calculate the change in entropy if 100 kJ of energy transfer as heat to

a large mass of water at (a) 0°C (273 K) (b) 100°C (373 K).
𝑞𝑟𝑒𝑣 𝑞𝑟𝑒𝑣
Sol: a) ΔS = b) ΔS =
𝑇 𝑇
100x1000 J 100x1000 J
ΔS = ΔS =
273K 373K
-1
ΔS = +366 JK ΔS = +268 JK-1
∴The increase in entropy is greater at the lower temperature.
Practical application of entropy in Heat engines

Suppose that the hot source is at a temperature Thot. Then when energy |q| is released from
it reversibly as heat, its entropy changes by -|q|/Thot
Suppose that we allow an energy |q′| to flow reversibly as heat into the cold sink at a
temperature Tcold.
Then the entropy of that sink changes by +|q'|/Tcold
The total change in entropy is ∴ΔStotal = -|q|/Thot +|q'|/Tcold

The engine will not operate spontaneously if this change in entropy is negative, and just
becomes spontaneous as ΔStotal becomes positive.
This change of sign occurs when ΔStotal = 0 which is achieved
when
|𝑞′|= |q| x
Tcold 33
Thot
If we have to discard an energy |q′| into the cold sink, the

maximum energy that can be extracted as work is |q| −
|q′|.
It follows that the efficiency, η(eta), of the engine, the ratio
of the work produced to the heat absorbed, is
𝑤𝑜𝑟𝑘 𝑝𝑟𝑜𝑑𝑢𝑐𝑒𝑑 |𝑞|−|𝑞 ′ | |𝑞 ′ |
η= = |𝑞|
=1- |𝑞|
=1 – (Tcold/Thot)
ℎ𝑒𝑎𝑡 𝑎𝑏𝑠𝑜𝑟𝑏𝑒𝑑
The flow of energy as heat from a cold source to a hot sink becomes feasible if work is
provided to add to the energy stream. Then the increase in entropy of the hot sink can be
made to cancel the entropy decrease of the hot source.
This remarkable result tells us that the efficiency of a perfect heat engine depends only on
the temperatures of the hot source and cold sink. It shows that maximum efficiency (closest
to η = 1) is achieved by using a sink that is as cold as possible and a source that is as hot as
possible.
Prob. 2, Calculate the maximum efficiency of an electrical power station using

steam at 200°C (473 K) and discharging at 20°C (293 K).
293𝐾
Sol: η = 1 - 473𝐾
293
= 1 - 473
= 0.381 or 38.1 per cent
Practical application of entropy in Refrigerators, and Heat pumps

A refrigerator can be analysed similarly.
The entropy change when an energy |q| is withdrawn reversibly as heat from the cold interior
|𝐪|
at a temperature Tcold is − 𝐓
𝐜𝐨𝐥𝐝
The entropy change when an energy |q ′| is deposited reversibly as heat in the outside world
|𝐪′ |
at a temperature Thot is + 𝐓𝐡𝐨𝐭
The total change in entropy would be negative if |q′|=|q|, and the refrigerator would not
work. However, if we increase the flow of energy into the warm exterior by doing work on
the refrigerator, then the entropy change of the warm exterior can be increased to the point

at which it overcomes the decrease in entropy of the cold interior, and the refrigerator
operates.
A heat pump is simply a refrigerator, but in which we are more interested in the
supply of heat to the exterior than the cooling achieved in the interior.
34
The entropy change accompanying expansion
For a reversible isothermal expansion of a gas,
The amount of heat absorbed q = - w = - (-nRT ln Vf/Vi ) = nRT ln Vf/Vi
change in entropy when a perfect gas expands isothermally from a volume V i to a volume Vf,
and obtain
𝑛𝑅𝑇
ΔS = ln Vf/Vi
𝑇
ΔS = nR ln Vf/Vi
In this case:
𝑉𝑓
• If Vf > Vi, as in an expansion, then > 1 and the
𝑉𝑖
logarithm is positive. Consequently, above eqn.
predicts a positive value for ΔS, corresponding to an
increase in entropy.
• The change in entropy is independent of the
temperature at which the isothermal expansion
occurs. More work is done if the temperature is high Fig. The entropy of a perfect gas
so more energy must be supplied as heat to maintain increases logarithmically (as ln V) as
the volume is increased.
the temperature.
Prob.3: Calculate the change in molar entropy when a sample of hydrogen gas expands
isothermally to twice its initial volume.
Solution:
Vi = V; Vf = 2V; R = 8.314 J K-1 mol-1
ΔS = nR ln (Vf/Vi)
ΔS
Change in Molar entropy = R ln (Vf/Vi)
n
2V
= 8.314 J K-1 mol-1x ln ( V )
= 8.314 J K-1 mol-1 x 0.693

Change in Molar entropy = 5.7616J K-1 mol-1

The entropy change accompanying heating

• Equation 2.37 refers to the transfer of heat to a system at a temperature T. In general, the
temperature changes as we heat a system, so we cannot use eqn 2.37 directly.
• Suppose, however, that we transfer only an infinitesimal energy, dq, to the system, then
there is only an infinitesimal change in temperature and we introduce negligible error if 35
we keep the temperature in the denominator of eqn. 2.37 equal to T during that transfer.
As a result, the entropy increases by an infinitesimal amount dS given by
dS = dqrev /T Infinitesimal heat
Heat supplied
𝐶.𝑑𝑇 𝑞 𝑑𝑞
dS = (since C=∆𝑇 ; C = 𝑑𝑇; dq = C. dT)
𝑇
Rise in temp. Infinitesimal rise in Temp
The total change in entropy

𝑇𝑓 𝐶.𝑑𝑇
ΔS = ∫𝑇𝑖 𝑇
𝑇𝑓 𝑑𝑇
= C. ∫𝑇𝑖 𝑇
𝑇𝑓
ΔS = C. ln
𝑇𝑖
C is the heat capacity of the system; if the

pressure is held constant during the heating,
we use the constant-pressure heat capacity,
Cp, and if the volume is held constant, we use
the constant-volume heat capacity, CV. Fig. The entropy of a sample with a heat capacity that is
independent of temperature, such as a monoatomic perfect gas,
Once more, we interpret the equation: increases logarithmically (as ln T ) as the temperature is increased.
The increase is proportional to the heat capacity of the sample.
𝑇𝑓
When T𝑓 > T𝑖, 𝑇𝑖 > 1, which implies that the
logarithm is positive, that ΔS>0, and therefore that the entropy increases as the temperature
is raised.
The higher the heat capacity of the substance, the greater the change in entropy for a given
rise in temperature. A high heat capacity implies that a lot of heat is required to produce a
given change in temperature, so the ‘sneeze’ must be more powerful than for when the heat
capacity is low, and the entropy increase is correspondingly high.
Prob. 4: Calculate the change in molar entropy when hydrogen gas is heated from 20°C to
30°C at constant volume.(CV,m=22.44 J K−1 mol−1)
𝑇𝑓
Sol: ΔS= CV,m . ln 𝑇𝑖

303𝐾
ΔS= 22.44 J K−1 mol−1 . ln(293𝐾)
ΔS= 22.44 J K−1 mol−1 . ln(1.034)

ΔS= 22.44 J K−1 mol−1 . 0.03356
ΔS= 0.753 J K−1 mol−1 36
The entropy change when the heat capacity varies with temperature
When we cannot assume that the heat capacity is constant over the temperature range of
interest, which is the case for all solids at low temperatures, we have to allow for the variation
of C with temperature.
𝑇𝑓 𝐶.𝑑𝑇
ΔS = ∫𝑇𝑖 𝑇
In this case, the function is C/T, the heat capacity at

each temperature divided by that temperature.
We measure the heat capacity throughout the range
of temperatures of interest, and make a list of
values. Then we divide each one by the
𝐶
corresponding temperature, to get at each
𝑇
𝐶
temperature, plot these against T, and evaluate
𝑇
the area under the graph between the
temperatures Ti and Tf.
𝐶
ΔS = area under the graph of plotted against T, between Ti and Tf
𝑇
The simplest way to evaluate the area is to count squares on the graph paper, but a more
accurate way and the only reliable way in practice is to fit the data to a polynomial in T and
then to use a computer to evaluate the integral.
The entropy change accompanying a phase transition
We can suspect that the entropy of a substance increases when it melts and when it boils
because its molecules become more disordered as it changes from solid to liquid and from
liquid to vapour.
Moreover, the transition occurs at constant pressure, we can identify the heat transferred
per mole of substance with the enthalpy of fusion (melting).
Therefore, the entropy of fusion, ΔfusS, the change of entropy per mole of substance, at the
ΔfusH (Tf)
melting temperature, Tf (with f now denoting fusion), is ΔfusS = Tf
Prob 5: Calculate the standard entropy of fusion of ice at 0°C. (∆fusH of ice at 0oC = 6.01kJ/
mol) Answer: +22 J K−1 mol−1

The entropy of vapourisation, ΔvapS, the change of entropy per mole of substance, at the
boiling temperature, Tb (with b now denoting boiling), is
ΔvapS = ΔvapH at Tb/Tb
Prob. 6: Calculate the entropy of vaporization of water at 100°C. (ΔvapH = 40.7kJ mol-1)
Answer: +109 J K-1 mol-1
37
Trouton’s rule
• Etropies of vaporization shed light on an empirical relation known as Trouton’s rule.
∆𝐯𝐚𝐩𝐇(𝐓𝐛)
Trouton noticed that is approximately the same (and equal to about 85 J K-1mol-
𝐓𝐛
1)for all liquids except when hydrogen bonding or some other kind of specific molecular
interaction is present.
• This near equality is to be expected, because when a liquid vaporizes, the compact
condensed phase changes into a widely dispersed gas that occupies approximately the
same volume whatever its identity. To a good approximation, therefore, we expect the
increase in disorder, and therefore the entropy of vaporization, to be almost the same for
all liquids at their boiling temperatures.
A brief illustration
We can estimate the enthalpy of
vaporization of liquid bromine from its
boiling temperature, 59.2°C. No
hydrogen bonding or other kind of
special interaction is present, so we
use the rule after converting the
boiling point to 332.4 K:
ΔvapH = T . ΔvapS
= (332.4 K) × (85 J K−1 mol−1)
= 28 kJ mol−1
The experimental value is 29 kJ mol−1
Prob.7: Estimate the enthalpy of vaporization of ethane from its boiling point, which is
−88.6°C. Answer: 16 kJ mol −1
Calculating the entropy of vaporization

Prob.8: Calculate the entropy of vaporization of water at 25°C from thermodynamic data
and its enthalpy of vaporization at its normal boiling point. ΔvapH(Tb) = 40.7 kJ mol−1; Cp,m(l) =
75.29 J K−1 mol−1; Cp,m(g) = 33.58 J K−1 mol−1.
Most convenient way to proceed is to perform three calculations.

• First, calculate the entropy change for heating liquid water from 25°C to 100°C
• Then calculate ∆S as per ∆vapH.

• Next, calculate the change in entropy for cooling the vapour from 100°C to
25°C (accompanying heatcange).
• Finally, add the three contributions together.
• The steps may be hypothetical.
38
Sol:
Tf
ΔS1 = Cp,m(H2O liquid) ln Ti
373K
= 75.29 J K-1mol-1 x ln 298K
ΔS1 = +16.9 J K-1mol-1

ΔvapH(Tb) 40.7 x 103J mol-1
ΔS2 = = = +109 J K-1mol-1
Tb 373 K
Tf
ΔS3 = Cp,m(H2O vap) ln Ti = ΔS1
298 K
= 33.58 J K-1mol-1 x ln 373 K
= -7.54 J K-1 mol-1

The sum of the three entropy changes is the entropy of transition at 25°C
ΔvapS (298 K) = ΔS1 + ΔS2 + ΔS3
= +75.29 + 109 + (-7.54)
= +118.36 J K-1 mol-1
Prob. 9: Calculate the entropy of vaporization of benzene at 25°C from the following
data: Tb = 353.2 K; ΔvapH(Tb) = 30.8 kJ mol−1; Cp,m(l) = 136.1 J K−1 mol−1; Cp,m(g) =
81.6 J K−1 mol−1. Answer: 96.4 J K−1 mol−1
Entropy changes in the surroundings

qsur, rev
ΔSsur = T
qsur
ΔSsur = (since qsur,rev = ΔHsur = qsur)
T
q
ΔSsur = - T (since qsur = -q)
Vf
ΔSsur = - nR lnV
i
For a process at constant pressure,

ΔH
ΔSsur = - (since q = ΔH)
T

Prob. 10: A typical resting person heats the surroundings at a rate of about 100 W. Estimate
the entropy he generate in the surroundings in the course of a day at 20°C.
Course of a day is q = (86 400 s) × (100 JS-1) = 86 400 × 100 J
sur
The increase in entropy of the surroundings is therefore

39
q 86400 x 100 J 4J
ΔS = sur = = +2.95 x 10 K-1
sur T 293K
Prob. 12: Suppose a small reptile operates at 0.50 W. What entropy does it generate in the
course of a day in the water in the lake that it inhabits, where the temperature is 15°C ?
Answer: +150 J K-1
Change in Entropy in isothermal and isobaric process

At isothermal process, ΔT = 0
Vf Pi
Therefore, ΔST = nR ln V = nR ln Pf
i
At isobaric, isochoric process, ΔP = ΔV =0

Tf
Therefore, ΔSp = Cp ln T
i
Tf
ΔSV = CV ln T
i
Change in Entropy in chemical process
ΔrxnS = Δ ∑𝑝𝑟𝑜𝑑𝑢𝑐𝑡𝑠 𝑆 − 𝛥 ∑𝑟𝑒𝑎𝑐𝑡𝑎𝑛𝑡𝑠 𝑆
Change in Standard Entropy in chemical process
ΔrxnS0 = Δ ∑𝑝𝑟𝑜𝑑𝑢𝑐𝑡𝑠 𝑆 0 − 𝛥 ∑𝑟𝑒𝑎𝑐𝑡𝑎𝑛𝑡𝑠 𝑆 0
Prob. 13: Determine the overall change in entropy for the following process using 1.00 mole
of He: He (298.0 K, 1.50 atm)→He (100.0 K, 15.0 atm) The heat capacity of He is 20.78 Jmol-
1K-1. Assume the helium acts ideally.
Sol:
The overall reaction can be divided into two parts:
Step 1: He (298.0 K, 1.50 atm) → He (298.0 K, 15.0 atm) (change in pressure step)
Step 2: He (298.0 K, 15.0 atm) → He (100.0 K, 15.0 atm) (change in temp. step)
ΔS1= - nR ln Pf/Pi
15.0atm
ΔS1 = - (1.00 mol)(8.314 Jmol-1K-1) ln 1.50atm
ΔS1 = -19.1 J K-1

T 100 𝐾
ΔS2 = n C ln Tf = (1.00 mol)(20.78 Jmol-1) ln 298 K
i
ΔS2 = -22.7 J K-1

ΔS = -19.1 + (-22.7) JK-1= - 41.8 JK-1

Third Law of thermodynamics
The entropies of all perfectly crystalline substances are the same at T = 0.
For convenience, we take this common value to be zero. Then, with this convention, according
to the Third Law, S(0) = 0 for all perfectly ordered crystalline materials. 40
Entropies close to T = 0
𝑇𝑓 𝐶𝑝,𝑚 . 𝑑𝑇
ΔS = S(Tf) – S(Ti) = ∫𝑇𝑖 𝑇
=S(Tf) – S(0) = ∫0 since Ti = 0
𝑇
S(Tf) = ∫0 𝑇
according to the Debye T3-law, Cp,m = aT3, so

𝑇𝑓 𝑎𝑇3. 𝑑𝑇
S(Tf) = ∫0 𝑇
Tf
S(Tf) =a ∫0 T2. dT
At this point we can use the standard integral

1
∫ 𝑥2 𝑑𝑥 = 3 x3 + constant
1
S(Tf) =3 aT3
1
S(Tf) =3 Cp,m(T)
Free Energy: The Gibbs Function

ΔStot = ΔSsur + ΔSsys
ΔH q ΔH
ΔStot = - + Δssys since, We knew that ΔSsur = - T = -
T T
TΔStot = - ΔH + TΔSsys
-TΔStot = ΔH – TΔSsys
If –TΔStot is denoted by ‘ΔG’ Gibbs free energy change for the process.
ΔG = ΔH – TΔSsys
∴ Gibbs function is defined as G = H-TS

Standard free energy change in chemical reactions:
free energy change of a chemical reactions when the reactants and products in standard
states(25oC, 1 atm pressure). ΔGo = ΔHo – TΔSo

Prob. 14: Calculate the standard free energy change of the following reaction at 298 K and 1
atm pressure:
1
CO(g) + 2O2(g) → CO2(g) ΔHo = -282.84 kJ
Standard entopy of CO(g) is 197.90, O2(g) is 205.01 & CO2(g) is 213.80 JK-1mol-1
41
Sol:
ΔSo = ΔSoproducts - ΔSoreactants = 213.80 – (197.90 + 102.5) = -86.6JK-1
ΔGo = ΔHo – TΔSo
ΔGo =-282840 J– (298 K x -86.6JK-1) = - 282840 + 25806.8
ΔGo : -257.0332kJ
Prob. 15: Calculate the standard free energy change of the following reaction.
1 1
H 2(g) + I2(s) → HI(g) ΔHo = -25.95 kJ
2 2
Standard entopy of HI(g) is 206.27, H2(g) is 206.27 & I2(s) is 116.73 JK-1mol-1
Ans: -39291J
References
1. Elements of Physical Chemistry, fifth edition © 2009 by Peter Atkins and Julio De Paula,
2. Physical Chemistry, Second Edition, David W. Ball,
3. Principles of Physical Chemistry by Puri, Sharma and Pathania, Shobal Lal Nagin Chand
& Co Educational Publishers.
4. A Text Book of Engineering Chemistry, Shashi Chawla, Dhanpath Raj and Co.
5. http://www.chem1.com/acad/webtext/thermeq/TE4.html
6. http://elearning.vtu.ac.in/06ME33.html
7. https://www.youtube.com/watch?v=lbPEaaKiCww
8. Other internet sources

Chemical Kinetics
Rate Laws, Order, Rate Constants, Arrhenius Equation, Rate-determining step, Reaction mechanisms
The study of rates of chemical reactions and the factors influence the rate of reactions. 42
The definition of rate
Change in [J]
|𝛥[𝐽]| I . . . I means ignore

Rate = any negative sign
𝛥𝑡
Time interval of interest
|d[J]|
Rate v = dt
(NH2)2CO(aq) + 2 H2O(l) →2 NH4+(aq) + CO32−(aq)

Rate of formation of NH4+ = 2 × rate of consumption of (NH2)2CO
1 |d[J]|
Rate v = Vj d𝑡
stoichiometric numbers,
Prob. 1. The rate of formation of NH3 in the reaction N2(g) + 3 H2(g) → 2 NH3(g) was reported
as 1.2 mmol dm−3 s−1 under a certain set of conditions. What is the rate of consumption of H2?
Ans: 1.8 mmol dm−3 s−1
Rate laws and rate constants
The dependence the rate of a reaction on the concentration terms of the reactants is known
as the rate equation or rate law.
For ex. A + B → products, the rate of reaction is directly proportional to the molar
concentrations of the reactants. ∴ v = kr [A][B]
Prob. 2. The rate constant for the reaction O(g) + O3(g) →2 O2(g) is 8.0 × 10−15 cm3 molecule−1
s−1 at 298 K. Express this rate constant in dm3 mol−1 s−1.
We make use of
1dm
1 cm = 10−2 m = 10−2 × 10 dm = 10−1 dm = or 1cm3 = 10-3 dm3
10
1 mol
1 mol = 6.022 × 1023, so 1 molecule = 6.022 × 1023
Ans: 4.8 x 106 dm3 mol−1 s−1

Prob. 3. A reaction has a rate law of the form kr[A]2[B]. What are the units of the rate constant
k if the reaction rate was measured in mol dm−3 s−1?
Answer: dm6 mol−2 s−1
Factors influence the rate of reaction
1. Concentration of the reactants 43
2. Temperature
3. Nature of the reactants and products
4. Catalyst
5. Radiations
6. Surface area of the reactants
Reaction order (n)
For the reaction xA + yB  mC + nD
Rate  k[A]x[B]y rate law or rate equation
• Sum of the powers of the concentration terms in the rate equation of the reaction is
the order of the reaction.
The order for the above equation n = x+y.
Zero order
The reaction in which the rate is independent of concentration terms is called zero order
rection.
Ex. H2+Cl2 → 2HCl;
v = k[H2]o[Cl2]o and
n = 0+0 = 0
First order
1
N2O5(g) → N2O3(g) + 2O2(g); v = k[N2O5]1 and n=1
SO2Cl2(g) → SO2(g) + Cl2(g); v = k[SO2Cl2]1 and n=1
Second order
2N2O(g) → 2N2(g) + O2(g) ; v = k[N2O]2 and n=2
2 Cl2O(g) → 2 Cl2(g) + O2(g) ; v = k[Cl2O]2 and n=2
H2(g) + I2(g) → 2HI(g) ; v = k[H2][I2] and n=2
NO2(g) + CO(g) → NO(g) + CO2(g); v = kr[NO2]2 n= 2
Third order
2NO(g) + O2(g) → 2NO2(g) ; v = k[NO]2[O2] and n=3
Fractional order
3
CH3CHO(g) → CH4(g) + CO(g) v = k[CH3CHO]3/2 and n = 2
Pseudo Order

C12H22O11 + H2O (excess) → C6H12O6 + C6H12O6; v = k[C12H22O11] and n = 1

Molecularity
The number of atoms or ions or molecules participating in the elementary step of the reaction
is known as the molecularity of that reaction step.
Molecularity of the reaction cannot be zero or fractional. 44
It can be one, two or three.
It is deduced or inferred from the reaction mechanism.
1
N2O5(g) → N2O3(g) + 2O2(g); molecularity = 1
2N2O(g) → 2N2(g) + O2(g) ; molecularity = 2

2NO(g) + O2(g) → 2NO2(g); molecularity = 3
Reaction Mechanism
As per the schematic diagram of reaction
mechanism, Step S3 is the rate
determining step in both case of
mechanisms.
For assigning mechanism, proceed as
follows.
1. Experimentally, find out rate law
of that reaction
2. From the rate law, write the
slowest step, rate law tells us the
molecularity and order of the slowest step.
3. Predict the other fast steps in such a way so that on adding all those steps, we get the
original equation for the complex reaction.
First order reactions – Integrated Rate equation for a first order reaction
A first order reaction is an exponential process and the concentration of the reactant
decreases exponentially with time. Let us consider the following reaction which is of first order.
A → products
If, [R]0 = initial concentration of A, and [R] = concentration of A after a time interval of t , we
have Where, k is the rate constant of the reaction.
d[R]
- 𝛼 [R]
dt
d[R]
- = k[R]
dt

𝑡 d[R]
- ∫0 = ∫ 𝑘 𝑑𝑡
[R]
[𝑅]𝑡 [𝑅]0
k t = - ln [𝑅]𝑜 = ln [𝑅]𝑡
1 [𝑅]0
k = 𝑡 ln [𝑅]𝑡
45
2.303 [𝑅]0
k= log [𝑅]𝑡
𝑡
2.303 [R]o
k= log [R]
first order rate equation
𝑡
0.693
t1/2 = for first order rate equation
𝑘
[R] =[R]0 e –kt first order rate equation

Half-life period
The time in which the concentration of reactant is reduced to half of its initial value is called its
half-life period.
Prob. 4. The half-life of a substrate in a certain enzyme-catalysed first-order reaction is 138s.
How long is required for the concentration of substrate to fall from 1.28 mmol dm−3 to 0.040
mmol dm−3?
Ans: 690s
Prob. 5. In acidic solution, the disaccharide sucrose (cane sugar) is converted to a mixture of the
monosaccharaides glucose and fructose in a pseudo first order reaction. Under certain
conditions of pH, the half-life of sucrose is 28.4 min. Calculate how long it takes for the
concentration of a sample to fall from 8.0 mmol dm−3 to 1.0 mmol dm−3
Sol: 8.0 → 4.0 →2.0 →1.0
The total time required is 3 × 28.4 min = 85.2 min
Change of Concentration with Time
For 1st order reactions:
1 [R]0
k = 𝑡 ln [R]
t
[R]0
kt = ln [R]
t
[R]t
kt = - ln [R]
0
[R]t
- kt = ln [R]
0
ln[R]t = −kt + ln[R]0

This equation has the general form for a straight line, y=mx+b, so a plot of ln[A]t vs. t is a straight
line with slope (-k) and intercept ln[A]0.
Second-order integrated rate laws
2A → products; v = k[A]2 & n = 2
46
Half-life for second order reaction

Change of Concentration with Time

1 1
For 2nd order reactions: [A]t
= kt + [A]0
This equation has the general form for a straight line, y=mx+b,
so a plot of l/[A]t vs. t is a straight line with slope (k) and
47
intercept of 1/[A]0.
Third-order integrated rate laws
3A → products; v = k[A]3 & n = 3
Half-life for Third order reaction

Rate law for nth order reaction
48
Activation Energy
In other words, there is a minimum amount of energy required for reaction: the activation
energy, Ea.
Just as a ball cannot get over a hill if it does not roll up the hill with
enough energy, a reaction cannot occur unless the molecules
possess sufficient energy to get over the activation energy barrier.
Reaction Coordinate Diagrams
For example:
CH3NC → CH3CN

It is helpful to visualize energy changes throughout a process on a reaction coordinate diagram

like this one for the rearrangement of methyl isonitrile.
• It shows the energy of the reactants and products (and, therefore, E).
• The high point on the diagram is the transition state.
49
• The species present at the transition state is called the activated complex.
• The energy gap between the reactants and the activated complex is the activation
energy barrier.
Arrhenius Equation
Svante Arrhenius developed a mathematical relationship between k and Ea: k = A∙e-Ea/RT
Where A is the frequency factor, a number that represents the likelihood that collisions would
occur with the proper orientation for reaction.
Taking the natural logarithm of both sides, the equation becomes
𝐸𝑎
ln (k) = - 𝑅𝑇 + ln A
When k is determined experimentally at several temperatures, Ea

can be calculated from the slope of a plot of ln k vs. 1/T.
Prob. 6. What is the half-life of N2O5 if it decomposes with a rate constant of 5.7 x 10-4 s-1?
0.693 0.693
Sol. T1/2 = = 5.7 x 10-4 s-1 = 1200 s = 20 min
k
Prob. 7. Find oout the order of the raction from the following rate laws.
i) v = k[A]2[B] ii) v = k[A]1/2 [B][C] iii) k = [A]
1 1
Ans: i) 2+1 = 3 ii) 2 +1+1 = 22 iii) 1
Prob. 8. The catalyst decomposition of hydrogen peroxide in aqueous Solution, which is of first
order, is followed by titrating equal volumes of samples of the solution with potassium
permanganate at stated times as follows:
time in minutes. 0 5 15 25 45
mL of KMnO4 37 29.8 19.6 12.3 5.0
Calculate the constant of the reaction.
Sol:
for all the steps [R]0 = 37 and [R] values are varied
2.303 [𝑅]0
For first order reaction, k = log [𝑅]𝑡
𝑡
2.303 37 2.303 37
i) k = log 29.8 = 0.04339 min-1; ii) k = log 19.6 = 0.04236 min-1
5 15

2.303 37 2.303 37
iii) k = log = 0.04407 min-1; iv) k = log = 0.04447 min-1
25 12.3 45 5
The average value of k = 0.04353 min-1

Prob. 9. From the following data for the decomposition of ammonium nitrate in aqueous
solution, show that the decomposition of ammonium nitrate is of the first order reaction.
50
time in minutes. 10 15 20 25 ∞
volume of N2 in mL 6.25 9.0 11.4 13.65 35.05
Sol:
NH4NO2 → N2 + 2H2O There fore the concentration of N2 at ∞ is the concentration of
NH4NO2 at initial time i.e.. [R]0 = V∞ = 35.05 ml
2.303 [R]0
For first order reaction, k = log [R]t
t
i) 0.01964 min-1 ii) 0.01978 min-1 iii) 0.01967 min-1 iv) 0.01973 min-1
All the rate constant values are closer to each other. Hence the reaction is first order.
Prob. 10. The optical rotation of sucrose in 0.5N hydrochloric acid at 380K and at various time
intervals are given below.
time in min. 0 10 20 30 40 ∞
N +32.4 +28.8 +25.5 +22.4 +19.6 -11.1
Find out the order of the reaction.

Prob. 11. A first order reaction is 50% complete in 100 min. how long will it take for 90%
0.693
completion. T1/2 = 100 min. k = 100𝑚𝑖𝑛
Sol.
2.303 [R]0
As per first order reaction, t = log [R]t
k
[R]0 = 100 [R] after completion of 90% = 100-90 = 10

2.303 100
Therefore t= 0.693 log 10
100𝑚𝑖𝑛
2.303𝑥100𝑚𝑖𝑛
t= ∙ log 10
0.693
t = 332.3232 min
3
Prob. 12. 4th of a reaction of first order was completed in 10 min. calculate half-life period of
this reaction.
Sol:
3
t = 10 min = 600 sec; x = 4
2.303 [R]0
k= log [R]t
t

3 1
Suppose, as per the data, [R]0 = a; [R]t = a - a = a
4 4
2.303 a
k= log 1
600 a
4
2.303
k= log 4 = 2.31 x 10-3 sec-1
600
51
t1/2 = 0.693/0.00231 = 300 sec.
Prob. 13. show that the time taken for 99% of the first order reaction to take place is twice the
time required for 90% of the reaction.
Sol.
2.303 [R]0
k= log [R]t ;
t
Suppose, as per the data,

[R]0 = a; [R]t = a - 0.99𝑎 = 0.01 a
2.303 a
t99% = log 0.01a
k
2.303
t99% = log 100
k
2.303
t99% = x2 -------(1)
k
2.303 [R]0
k= log [R]t ;
t
Suppose, as per the data,

[R]0 = a; [R]t = a - 0.90𝑎 = 0.10 a
2.303 a
t90% = log 0.1a
k
2.303
t90% = log 10
k
2.303
t90% = x1 ------- (2)
k
Deviding (1) by (2), we get,
Therefore the time taken for 99% of the first order reaction to take place is twice the time
required for 90% of the reaction.

References
1. Elements of Physical Chemistry, fifth edition © 2009 by Peter Atkins and Julio De Paula,
2. Physical Chemistry, Second Edition, David W. Ball,
3. Principles of Physical Chemistry by Puri, Sharma and Pathania, Shobal Lal Nagin Chand & Co Educational
Publishers.
4. A Text Book of Engineering Chemistry, Shashi Chawla, Dhanpath Raj and Co.
5. http://uwf.edu/royappa/basicpchem/reaction_orders.doc 52
6. www.ilc.edu.hk/SubjectWeb/ChemWeb/Ppt/Ch14%20(EE).ppt
7. http://www.ilc.edu.hk/SubjectWeb/ChemWeb/Ppt/Ch14%20%28EE%29.ppt
8. osf1.gmu.edu/~jschreif/212/Overheads/Ebbing14.ppt
9. http://chemistry.about.com/od/lecturenotesl3/a/reactionorder.htm
10. http://staff.um.edu.mt/jgri1/teaching/che2372/notes/07/01/det_rate_laws.html
11. http://exchange.smarttech.com/details.html?id=ab1b2508-0772-4d9e-a965-f4e9c0dc1bba


Unit Ii - Thermodynamics

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Unit Ii - Thermodynamics

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Unit – II: THERMODYNAMICS

Thermodynamic Systems, State Functions, Thermal Equilibrium and Temperature, Work,

More specifically, thermodynamics deals with

(a) Energy conversion and (b) the direction of change.

The third law defines the absolute zero of entropy.

System: The part of the universe that we choose to study

Surroundings: The rest of the universe. (or) mass or

Boundary: The surface dividing the system from the

Dr. K. Chandramohan, Assistant Professor, Department of Chemistry, MITS, Madanapalle-517325

Intensive : Independent on mass of system.

Specific Extensive properties per unit mass.

Dr. K. Chandramohan, Assistant Professor, Department of Chemistry, MITS, Madanapalle-517325

Some values of system properties have nothing to do with

State function is defined as “a property of thermodynamic

Ex. Pressure, temperature, volume and energy.

Process: Any change a system undergoes from one

Series of states through which system passes during the

Dr. K. Chandramohan, Assistant Professor, Department of Chemistry, MITS, Madanapalle-517325

If the path is not infinitesimally close to equilibrium conditions

Types of Thermodynamic Processes

Any of the state function or perticular property remains

Isobaric process: A process during which the pressure P

Isochoric (or isometric) process: A process during which the

Isothermal process: A process during which the temperature

Isenthalpic process: A process during which the enthalpy H

Isentropic process: A process during which the entropy S

Dr. K. Chandramohan, Assistant Professor, Department of Chemistry, MITS, Madanapalle-517325

1. Celsius Scale ( ºC ) – SI System

Thermodynamic Temperature Scale – Kelvin scale

Definition: Normal Force exerted by a fluid per unit Area.

Absolute Pressure: Actual Pressure at a given position. It measured relative to absolute

Gauge Pressure: Pressure more

Vacuum Pressure: Pressure less

Dr. K. Chandramohan, Assistant Professor, Department of Chemistry, MITS, Madanapalle-517325

Zeroth Law of Thermodynamics

If object A is in thermal equilibrium with object B, and object B is separately in thermal 6

Ex. Hot cup of tea or coffee, cool drink

Work has units of joules, like energy.

James Joule, 1980 showed that W 𝛼 H or w = JH -------(2.2)

Where w is work done; H is heat produced; J is Joule mechanical equivalent of heat.

Here J = 4.184 X 107 ergs = 4.184 J =1 calorie.

Dr. K. Chandramohan, Assistant Professor, Department of Chemistry, MITS, Madanapalle-517325

Heat energy = temperature (Intensity factor) X heat capacity (capacity factor)

When a current flows in in an electric circuit for a given interval of time,

When ‘m’ kg mass of moved through a height of ‘h’ m,

dw = -pext dV ----------------- (2.4)

w = -∫ 𝐩𝐞𝐱𝐭 𝐝𝐕 ---------- (2.5)

If pext is the constant throughout the process,

Dr. K. Chandramohan, Assistant Professor, Department of Chemistry, MITS, Madanapalle-517325

a. First, the change in volume is needed. We find it as follows:

ΔV = Vf - Vi = 5.50 L - 2.00 L=3.50 L

w = - Pext ΔV = -(1.75 atm)(3.50 L) = -6.13 L atm

Dr. K. Chandramohan, Assistant Professor, Department of Chemistry, MITS, Madanapalle-517325

(2.00 L)(8.00 atm) = (5.50 L)(Pf) Pf = 2.91 atm

Work done on free expansion

work = 0 for free expansion

c. Gaseous CHF2Cl, a refrigerant, is compressed in the compressor of an air conditioner, to

Reversible, isothermal expansion work

Reversible or irreversible processes can be explained based on volume changes, temperature

Pext = Pint for reversible change.

Dr. K. Chandramohan, Assistant Professor, Department of Chemistry, MITS, Madanapalle-517325

The following substitution can then be made for reversible changes

wrev =-∫ Pint dV ------(2.7)