Engineering Chemistry

Module -1

A. Thermodynamics
Laws of thermodynamics - entropy change (selected processes) – spontaneity of
a chemical reaction and Gibbs free energy - heat transfer;
Kinetics - Concept of activation energy and energy barrier - Arrhenius equation-
effect of catalysts (homo and heterogeneous) – Enzyme catalysis (Michaelis-
Menten Mechanism).

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 Thermodynamics: Basic Terminologies

the quantity of matter or a region Properties of a system:

Thermodynamic Systems: in space upon which attention is # Intensive Properties:
concentrated in the analysis of a
problem
Everything
external to
the system

# Extensive Properties

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 Thermodynamics: Basic Terminologies

Internal energy (U)

# State function: = Kinetic energy + Potential energy
Depends on the initial state & final state;
independent of the path used to reach from. • It’s a state function & an extensive property of
Example: T (Temperature), P (Pressure), U (Internal the system.
energy), H (Enthalpy) etc. • Internal energy of a system changes when energy
is transferred into or outside the system in the
form heat or work

Ø 𝜟𝑼𝒔𝒚𝒔𝒕𝒆𝒎 = 𝑼𝒇𝒊𝒏𝒂𝒍 𝒔𝒕𝒂𝒕𝒆 −

# Path function: 𝑼𝒊𝒏𝒊𝒕𝒊𝒂𝒍 𝒔𝒕𝒂𝒕𝒆
Depends on the path between the initial & final state
Example: W (work done), q (heat transferred) etc. 3
Viewed at a molecular level, the internal energy can take on a number of forms such as

• the translational energy of the molecules.

• the potential energy of the constituents of the system; for example, a crystal consisting of
polarizable molecules will experience a change in its potential energy as an electric field
is applied to the system.
• the internal energy stored in the form of molecular vibrations and rotations.
• the internal energy stored in the form of chemical bonds that can be released through a
chemical reaction.
• the potential energy of interaction between molecules.

The total of all these forms of energy for the system of interest is given the symbol U and is
called the internal energy

The internal energy U of an isolated system is constant

 Thermodynamics: Basic Terminologies
State of a system
Ø The state of thermodynamic variables such as pressure, temperature, volume, composition
which describes the system is called state of the system.
Ø when one/more variables undergo change, the system is said to have undergone a change
of state

• Adiabatic – no heat transferred

• Isothermal – constant temperature
• Isobaric – constant pressure
• Isochoric – constant volume
 REVERSIBLE AND IRREVERSIBLE PROCESSES
• A thermodynamic reversible process is one that takes place infinitesimally
slowly and its direction at any point can be reversed by an infinitesimal change
in the state of the system.

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 Sign Convention of Heat
The symbol of heat is q. If the heat flows from the surroundings into the system to raise the energy of the system, it
is taken to be positive, +q. If heat flows from the system into the surroundings, lowering the energy of the system,
it is taken to be negative, –q

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 Sign Convention of Work
The symbol of work is w. If work is done on a system by the surroundings and the energy of
the system is thus increased, it is taken to be positive, +w. If work is done by the system on
the surroundings and energy of the system is decreased, it is taken to be negative, –w.

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 Work Done by a System
A force created from any source can do work by moving an object through a displacement

A gas confined to a cylinder that has a movable piston at

one end. If the gas expands against the piston, it exerts a
force through a distance and does work on the piston.
If the piston compresses the gas as it is moved inward, work
is also done—in this case, on the gas.

Let the gas pressure on the piston face be p. Then the force on
the piston due to the gas is pA, where A is the area of the face.
When the piston is pushed outward an infinitesimal
distance dx, the magnitude of the work done by the gas is

Since the change in volume of the gas is dV=Adx, this becomes dW = pdV.

9
For a finite change in volume from V1 to V2, we can integrate this equation from V1 to V2to find
the net work:
 Reversible Process in Thermodynamics
# Example 1:
q A thermodynamics process is
Thermal equilibrium of two systems with the same temperature
reversible if the process can be
§ If the temperature of either system is lowered infinitesimally,
turned back such that both the
then energy flows into the system with the lower temperature.
system and the surroundings
§ If the temperature of either system at thermal equilibrium is
return to their original states,
raised infinitesimally, then energy flows out of the hotter system
with no other change
anywhere else in the universe. # Example 2:
Reversible expansion:
Ø In reality, no such processes as Suppose a gas is confined by a piston.
reversible processes can exist. external pressure (Pex) = pressure (P) of the confined gas.
Thus, a more appropriate § Such a system is in mechanical equilibrium with its surroundings
definition is a reversible change because an infinitesimal change in the external pressure in either
in thermodynamics is direction causes changes in volume in the opposite directions.
A change that can be reversed by an dw = −𝑃𝑒𝑥𝑑𝑉 = −𝑝𝑑𝑉
infinitesimal modification of a variable. !
W = − ∫! " 𝑝dv
!

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 0th Law of Thermodynamics

Ø According to 0th law:

If two systems are in thermal equilibrium with a third system,
then those two systems are in thermal equilibrium with each
other.

q Two physical systems are in thermal

equilibrium if there is no net flow of
heat (thermal energy) between
them when they are connected by a
path permeable to heat.

Ø The 0th law of thermodynamics defines thermal equilibrium and

forms a basis for the definition of temperature.

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 1st Law of Thermodynamics

§ It’s the law of conservation of energy

q The energy of an isolated system remains constant. Whenever a quantity of energy (some form)
disappears, an exactly equivalent quantity of energy (some other form) must make an appearance.

Ø Heat (q) and work (w) are equivalent ways of changing the internal energy of a system
® Example:
o If a weight has been raised/lowered in the surroundings, transfer of energy happens by doing the work.
o If ice has melted in the surroundings, it indicated transfer of energy as heat.

Ø For a system, if w = work done on a system, q

= energy transferred as heat to a system & 𝜟𝑼 = 𝒒 + 𝒘
ΔU = resulting change in internal energy
The sign of w and q:
ü +ve if energy is transferred to the system as work/heat
ü -ve if energy is lost from the system.
Therefore,
change in internal energy (𝛥𝑈 ) of a system = heat added to the system (q) - the work done by the system (w)

𝜟𝑼 = 𝒒 − 𝒘 13
Other Definitions of First Law of Thermodynamics
(1) Whenever energy of a particular type disappears equivalent amount of another type
must be produced.
(2) Total energy of a system and surroundings remains constant (or conserved)
(3) It is impossible to construct a perpetual motion machine that can produce work without
spending energy on it

Mathematical statement of the First law of Thermodynamics is

ΔE = q – w

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 Some Special Forms of First Law of Thermodynamics

Case 1 : For a cyclic process involving isothermal expansion of an ideal gas

ΔE = o
∴q=w

Case 2 : For an isochoric process (no change in volume) there is no work of expansion i.e.
w = 0. Hence
ΔE = q
Case 3 : For an adiabatic process there is no change in heat gained or lost i.e. q = 0. Hence
ΔE = – w
In other words, the decrease in internal energy is exactly equal to the work done on the system
by surroundings

Case 4 : For an isobaric process there is no change in pressure, i.e. P remains constant. Hence
ΔE = q – w
or ΔE = q – PΔV
ENTHALPY OF A SYSTEM
In a process carried at constant volume (say in a sealed tube), the heat content of a system is
the same as internal energy (E), as no PV work is done.
But in a constant-pressure process, the system (a gas) also expends energy in doing PV work.
Therefore, the total heat content of a system at constant pressure is equivalent to the
internal energy E plus the PV energy.
This is called the Enthalpy (Greek en = in; thalpos = heat) of the system and is represented by
the symbol H.
Thus
enthalpy is defined by the equation : H = E + PV

If P is constant while the gas is expanding, we can write

ΔH = ΔE + PΔV
or ΔH = ΔE + w (w = work) …..(1)

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Enthalpy is the heat at constant pressure

According to the First Law,

ΔE = q – w ...(2)
where q = heat transferred
From equations (1) and (2)
ΔH = q when change in state occurs at constant pressure
This relationship is usually written as
ΔH = qp
where subscript p means constant pressure.
Thus Δ H can be measured by measuring the heat of a process occurring at
constant pressure

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 Enthalpy & Heat Capacity

Ø If the change of a system is brought about at q Heat capacity (C) of a system b/n any two temperatures –
constant pressure, there will be change in the quantity of heat (q) required to raise the temperature
volume. of the system from the lower temperature (T1) to the higher
temperature (T2) divided by the temperature difference.
Vi = volume of initial state, Vf = volume of final state. 𝒒
Work done by the system, 𝑤 = −𝑃 (𝑉" − 𝑉# ) 𝑪 =
𝑻𝟐 − 𝑻𝟏
\ΔU = q + w ☻ If mass of the system is 1 g,
or, ΔU = q - P (𝑉" − 𝑉# ) the heat capacity is called the specific heat of the system
☻ For 1 mol of substance,
Þ 𝐸" − 𝐸# = q – P 𝑉" − 𝑉#
the heat capacity is termed as ‘molar heat capacity’
Þ (𝐸" + 𝑃𝑉" ) − 𝐸# + 𝑃𝑉# = 𝑞
&'
q The quantity (U + PV) is called the Ø Molar heat capacity varies with temperature C= &(
enthalpy (H) of the system
Þ 𝐻" − 𝐻# = 𝑞
q Molar heat capacity at constant volume
𝜕𝐸
ΔE = ΔH – PΔV 𝐶! =
𝜕𝑇 !
or, ΔH = ΔE + PΔV @ constant volume w = 0 & ΔU = q
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 Heat Capacity
q Molar heat capacity at constant pressure (Cp)
ΔE = q + w
@ constant pressure, 𝝏𝑯
there is change in volume ΔE = q – P (𝑉" − 𝑉# ) As quantity (U+PV) is the Þ 𝑪𝒑 =
or, q = ΔU + pΔV enthalpy (H) of the system 𝝏𝑻 𝒑
& some work is done

q Relationship between Cp & Cv § For ideal gas, PV = RT (for 1 mole)

Δ(PV) = R ΔT
For a system, ΔH = ΔE + Δ(PV)
ΔH ΔE Δ(PV) RΔ(T)
or, ΔT = ΔT + ΔT 𝐶+ = 𝐶! + or, 𝐶+ = 𝐶! + R
ΔT
Δ(PV) or, 𝑪𝒑 ― 𝑪𝒗 = R
or, 𝑪𝒑 = 𝑪𝒗 + ΔT

CV = 3/2 R (For monoatomic ideal gas)

CP = 5/2 R (For monoatomic ideal gas)
𝑪𝒑
Heat capacity ratio, 𝜸 = = 5/3 for a monoatomic ideal gas
𝑪𝒗
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 Application of 1st Law to the Expansion Work

Ø Isothermal Process (constant temperature)

§ In an isothermal process, the
temperature stays constant,
so the pressure and volume
work done are inversely proportional
to one another

Þ For an ideal gas,

The internal energy (U) µ Temperature (T)
if T = fixed, ΔU = 0 (according to 1st law, which deals with ΔU)
Pressure-volume diagram As, 𝜟𝑼 = 𝒒 − 𝒘 = 𝟎
§ If the system does work, the energy comes
Þ q=w
from heat flowing into the system from
the surrounding
# Magnitude of w depends on whether the § if work is done on the system, heat flows
expansion is reversible or irreversible. out of the system to the surrounding.
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 reversible expansion. More work is obtained when the exp
ntegral can be evaluated once it is known how the pres- sion is reversible (the area is greater) because matching
of the confined gas depends on its volume. Equation external pressure to the internal pressure at each stage of
is the link with the material covered in Focus 1 because, process ensures that none of the pushing power of the sys
equation of state of the
Application ofgas
1stisLaw
known, p can
to the be expressed
Expansion Work is wasted. It is not possible to obtain more work than tha
ms of V and the integral can be evaluated.
Ø Reversible isothermal expansion: pi
sothermal reversible !expansion of a
!" -.(
p = nRT/V
"
w = ∫! 𝑃dv = ∫! dv (as PV = nRT)
ect gas

Pressure, p
! ! / pf
(throughout the expansion, Pex = P as the expansion is reversible)
der the isothermal reversible expansion of a perfect gas.
§ Work
xpansion done by
is made the n moles
isothermal by of gas canthe
keeping be evaluated
system inas:
mal contact with its unchanging /" surroundings
0 (which
w = −𝑛𝑅𝑇 ln / = −𝑛𝑅𝑇 ln 0 !
be a constant-temperature !bath). Because " the equation
/" 0 !
te is pV = nRT,
(since = at each
in stage
an p = nRT/V,
isothermal expansion V athe
with of vol- gas)
perfect Vi Volume, V Vf
/! 0!
at that stage of the expansion. The temperature T is con-
in an isothermal expansion, so (together with n and R) it Ø The work done by a perfect gas when it
Ø Relations for Irreversible Isothermal expansion pi
expands reversibly and isothermally pf
is equal
be taken outside the integral. It follows that the work of
ermal reversible expansion(expansion
of a perfectingas from Vi to Vf at to the area under the isotherm p = nRT/V.
a) Free expansion vacuum) Ø The work done during the irreversible
perature T isw = - !" 𝑃 dv =0 Figure 2A.7 The work done by a perfect gas when it expands
∫! 12 expansion against the same final pressure is
!
reversibly and isothermally is equal to the area under the isoth
a) Volume of the gas expands against a constant pressure. equal to the rectangular area shown slightly
Integral A.2
!"# !" p = nRT/V. The work done during the irreversible expansion aga
w = - 𝑃 dv = -P (V – V
∫! 12 V exWorkf of isothermal ) darker. Note that the reversible work done
V dV i the same final pressure is equal to the rectangular area shown
− nRT ∫ is greater than the irreversible work done.
f !
= − nRT ln f reversible expansion (2A.9)
V V
i Vi [perfect gas] slightly darker. Note that the reversible work done is greater th
the irreversible work done. 21
 Application of 1st Law to the Expansion Work
Ø Adiabatic process (constant heat) Ø Reversible adiabatic expansion
§ no heat is added/ removed from a system. § Relation between T, V and P
§ 1st law of thermodynamics: 345
𝑇# 𝑉"
ΔU = w = (! /"
𝑇" 𝑉# Þ ln = 𝛾 − 1 𝑙𝑛
(as no heat is allowed to enter/leave the system, q = 0) (" /!

𝑪𝒑 /" 𝐶+
ü Example: A gas expanding so quickly that no heat can be Þ ln
(!
= − 1 𝑙𝑛 [𝑎𝑠, 𝛾 = ]
transferred. Due to the expansion work, temperature (" 𝑪𝒗 /! 𝐶!
drops. This is exactly what happens with a carbon dioxide (! 𝑹 /"
fire extinguisher, with the gas coming out at high Þ ln = 𝑙𝑛 [𝑎𝑠, 𝐶+ ― 𝐶! = R]
(" 𝑪𝒗 /!
pressure and cooling as it expands at atmos. pressure
𝑻𝒊 𝑽𝒇
® Expansion: w = ― ve, ∆𝑼 = ― ve; Þ 𝑪𝒗 ln = 𝑹 𝒍𝒏
𝑻𝒇 𝑽𝒊
So, T of the system falls
Þ Work is done by the system at the expense of its Ø Irreversible adiabatic expansion
internal energy § Free expansion (Pex = 0) : ∆𝑇 = 0, 𝑊 = 0, ∆𝐻 = 0
§ w = ∆𝑈 = 𝑪𝒗 𝚫𝑻 (for 1 mole of gas) § Expansion against a constant pressure:
(! 0" 4(" 0!
§ ∆𝐻 = 𝑪𝒑 𝚫𝑻 (for 1 mole of gas) 𝐶! 𝑇" − 𝑇# = 𝑅 𝑃12
0! 0"
22
 Application of 1st Law to the Expansion Work
Ø Isobaric process (constant pressure) Ø Isochoric process (constant volume)

§ the pressure is kept constant. § the volume is kept constant

§ The work done by the system in an isobaric process is § The work done is zero in an isochoric process
simply the pressure multiplied by the change in
volume ü . Example of an isochoric system: A gas in a box
ü Example of an isobaric system: A gas, being slowly with fixed walls
heated or cooled, confined by a piston in a cylinder.

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 Numerical from of 1st Law

v Example 1: Calculate w and ∆𝑈 for the conversion of 1 v Example 2: 1 mole of an ideal gas expands against
mole of water at 100 ℃ to steam at 1 atm pressure. a constant external pressure of 1 atm from a
Heat of vaporisation of water at 100 ℃ is 40670 Jmol-1 volume of 10 dm3 to a volume of 30 dm3. Calculate
the work done by the gas in Joules.
Solution: Solution:
P = 1 atm = 101325 Nm-2 𝑤 = −𝑃𝑒𝑥𝛥𝑉
Vi = vol. of 1 mole of liquid water at 1 atm pressure = − 1 𝑎𝑡𝑚 30 𝑑𝑚9 − 10𝑑𝑚9
= 18 ml = 18 × 10-6 m3
= −20 𝑑𝑚9 𝑎𝑡𝑚
Vf = vol. of 1 mole of steam at 100 ℃ at 1 atm pressure
= (22.4 dm3 × 373)/273 = 30.60 dm3 = 0.0306 m3
w = P (Vf - Vi) R = 8.314 Jmol-1K-1 = 0.08206 dm3 atm K-1 mol-1
= 101325 Nm-2 [0.0306 m3-(18 × 10-6 )m3]
:.95< > ?@A '( B '(
= 101325 Nm-2 × 0.0306 m3 = 3100 Jmol-1 1 atm = C.C:DCE &? ) ?@A '( B '(
Since, conversion of water to steam is accompanied
by increase in volume, work is done by the system Therefore,
on the surroundings. 𝑤 = −20 𝑑𝑚9 𝑎𝑡𝑚
Hence, w = – 3100 Jmol-1
9 :.95< > ?@A '( B '(
= −20 𝑑𝑚 × = – 2026 J
C.C:DCE &? ) ?@A '( B '(
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 Numerical from of 1st Law

v Example 3: 1 mole of an ideal monoatomic gas at 27 oC expands reversibly and adiabatically from a volume of
F 9
10 dm3 to a volume of 20 dm3. Calculate q, ∆U, W and ∆H. Given * =
. D
Solution:
Since the process is adiabatic, q = 0 Since for an adiabatic process, q =0,
(" / hence ΔU = w = – 1384 J
𝐶! ln ( = 𝑅 ln / !
! " ΔH = ΔU + ΔPV = ΔU + ΔnRT
9 (" 5C &? ) = ΔU + nR(Tf- Ti)
Þ ln 9CC = ln(DC &? ) ) Þ Tf = 189K
D
® 𝑛𝑅 𝑇" − 𝑇#
𝜕𝑈 ® = (1 mol) 8.314 𝐽 𝑚𝑜𝑙 45 𝐾 45 189 − 300
𝐶! = Þ 𝑑𝑈 = 𝐶! 𝑑𝑇
𝜕𝑇 ! = −923 𝐽
For a finite change in n moles, ΔH = – 1384 J – 923 J = – 2307 J
∆𝑈 = 𝑛𝐶! ∆𝑇 # Note: ΔH can also be calculated by using the
9 45 45
= (1 mol) × 8.314 𝐽 𝑚𝑜𝑙 𝐾 (189 − 300)𝐾 relation 𝒅𝑯 = 𝑪𝒑 𝒅𝑻
D
= – 1384 J
v Example 4: 10 moles of an ideal gas expands reversibly and isothermally from a pressure of 10 atm to 2 atm at
300 K. Calculate the work done.
0! 5C GH?
Solution: w = −𝑛𝑅𝑇 ln = −(10 mol) 8.314 𝐽 𝑚𝑜𝑙 45 𝐾 45 300 𝐾 ln = − 40.15 × 10325J
0" D GH?