Chapter 2

The First Law

The First Law of Thermodynamics

• The First Law (Conservation of Energy)

– The energy can be transformed (changed from one form
to another), but it can neither be created nor destroyed
– No perpetual motion machine, a machine that does work
without consuming fuel or using some other source of
energy, has ever been built

• Thermodynamics
– The study of transformations of energy
 Transform of Energy
Examples
Fuel  Heat
Fuel  mechanical work (engine)
Chemical reaction  electricity (batteries)

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 Basic Concepts
• The Universe = System + Surroundings

• System
– the part of the world in which we have a special interest
• a reaction vessel
• an engine
• an electrochemical cell
• a biological cell

• Surroundings
– the region outside the system where we make our
measurements
 Various Systems

• Open system, a system with a boundary through which matter can

be transferred.
• Closed system, a system with a boundary through which matter
cannot be transferred.
• Isolated system, a system with a boundary through which neither
matter nor energy can be transferred.
 Work and Energy
• Work, the transfer of energy by motion against an opposing
force
– Raising a weight
– Expansion of a gas that pushes out a piston and raises a weight
– Chemical reaction that drives an electric current through a resistance
 passes through a motor and used to raise a weight

• Energy, the capacity to do work

– By compressing a gas or winding a spring, the capacity of the system to
do work is increased – energy of the system is increased
– When the system does work, the energy of the system is reduced, and
it can do less work than before
The energy of a system
may be changed by not
only work but also heat
Heat
Heat, the transfer of energy as a result of a temperature difference.
Hot water can be used to do more work than the same amount of cold water
• Exothermic process, a process that releases energy as heat. (e.g., combustion)
• Endothermic process, a process that absorbs energy as heat. (e.g., vaporization)
• Adiabatic boundary, a boundary that does not permit energy transfer as heat.
• Diathermic boundary, a boundary that permits energy transfer as heat.
• Thermal motion, the random motion of molecules.

Adiabatic Diathermic
 Molecular Interpretation
Heat Work

When energy is transferred to When a system does work, it

the surroundings as heat, the stimulates orderly motion in
transfer stimulates random the surroundings. For
motion of the atoms in the example, the atoms shown
surroundings here may be part of a weight
that is being raised
Thermal motion
Organized motion
the disorderly random motion of
of molecules
molecules
 Internal Energy
• Internal energy, the total energy of a system.
– Total kinetic energy & potential energy of molecules (or atoms/ions)

• The change in internal energy

– ∆U = Uf – Ui (change in internal energy)
– Ui : internal energy at an initial state
– Uf : internal energy at a final state

• State function, a property that depends only on the current state of the
system and is independent of how that state has been prepared.
– Internal energy is a state function: its value only depends on the current
state (not path)
 Unit of Internal Energy
• Unit of internal energy, heat & work: Joule
– 1 J = 1 kg·m2/s2 (a human heartbeat consumes about 1 J)
– 1 eV = 1.6× 10-19 J = 0.16 aJ
– 1 cal = 4.184 J exactly (raises the temp. of 1 g of water by 1 oC)

• Molar internal energy, Um = U/n

– Internal energy divided by the amount of substance in a system
– Unit = kJ/mol

• Extensive property
– A property that depends on the amount of substance present in the
sample (e.g. volume, internal energy)

• Intensive property
– A property that is independent on the amount of substance present
in the sample (e.g. mass density, ρ = m/V; molar internal energy)
 Internal Energy: Molecular
Interpretation
• A molecule has a certain number of motional degrees of
freedom
– Translate: the motion of its center of mass through space
– Rotate: around its center of mass
– Vibrate: bond lengths and angles change, leaving its center of mass
unmoved)

• Many physical and chemical properties depend on the energy

associated with each of these modes of motion
 Equipartition Theorem
(about average energy)
• In a sample at a temperature T, all quadratic
contributions to the total energy have the same
mean value, namely ½ kT

• A ‘quadratic contribution’ means a term that is

proportional to the square of the momentum or
the displacement from an equilibrium position

• Kinetic energy of a body of mass m free to

undergo translation, Ek = ½ mvx2 + ½ mvy2 + ½ mvz2

• Each term contributes ½ kT  3/2 kT

 Equipartition Theorem
• When the temperature is so high that many energy levels
are occupied, we can use the simple equipartition theorem
instead of Boltzmann distribution to calculate the average
energy

• The theorem is strictly valid only at high temperatures or if

the separation between energy levels is small because under
these conditions many states are populated

• Separation between vibrational and electronic states is

typically greater than for rotation or translation
 Equipartition Theorem
• Mean energy of atoms free to move in three
dimensions is 3/2 kT and total energy of a
monatomic perfect gas is 3/2 NkT or 3/2 nRT (N =
nNA and R = NAk)

• Um(T) = Um (0) + 3/2 RT (monatomic gas;

translation only)

• Internal energy of a perfect gas increases linearly

with temperature

• Um (0): The contribution to the internal energy

arises from the internal structure of the atoms
when T = 0K
 Rotation
• The gas consists of molecule -> needs to consider
rotation and vibration as well.

• Linear molecule (N2, CO2) can rotate around two

axes  two modes of rotation, each contributing a
term ½ kT  ½ NkT = ½ nNAkT = ½ nRT

• Um(T) = Um (0) + 5/2 RT (linear molecule;

translation and rotation only)

• Erot = ½ Iω2
• Etrans = ½ mυ2
 Rotation (Nonlinear Molecule)
• Nonlinear molecule (H2O, CH4) can rotate around
three axes  three modes of rotation contribute
3 * ½ kT 3/2 nRT

• Um(T) = Um (0) + 3 RT (nonlinear molecule;

translation and rotation only)

• As T is raised, U increases as the various modes of

motion become more highly excited
 Vibration
• Molecules do not vibrate significantly at room
temperature

• Separation between vibrational states is typically

greater than for rotation or translation 
equipartition theorem is unreliable

• The contribution of molecular vibrations to the

internal energy is negligible

• Except for very large molecules such as polymers

and biological macromolecules
 Internal Energy
• Internal energy, can be changed
– by doing work on the system
– by heating it

• First law of thermodynamics: the internal energy of

an isolated system is constant, ΔU = q + w.
– Isolated system:the internal energy is const.
• q = 0, w = 0  ΔU = 0
– Closed system: change of internal energy = heat + work
• If energy is transferred to the system as work or heat
• q > 0, w > 0  ΔU > 0 (system’s perspective)
• If energy is lost from the system as work or heat
• q < 0, w < 0  ΔU < 0
 Infinitesimal Change in U

• ΔU = w + q  dU = dw + dq
• dU: infinitesimal change in internal energy
• dw: Work done on the system
• dq: Energy supplied to the system as heat
 Expansion Work

• Expansion work: work arising from a change in

volume
– Work by a gas as it expands and drives back the
atmosphere
– Chemical reactions resulting in the generation or
consumption of gases

• Thermal decomposition
– CaCO3(s) → CaO(s) + CO2(g) (T > 840 °C)
 General Expression for Work
Work required to move an object a distance dz against an
opposing force of magnitude F

dw = -|F|dz
Internal energy decreases
If the external pressure is pex, the force is |F| = pexA
dw = -|F| dz = -pexAdz = -pexdV
Vf
w = −  p ex dV
Total work (Vi  Vf) Vi

The wall is
1. massless
2. frictionless
3. rigid
4. perfectly fitting the piston
Non-Expansion Work
(additional work)
Expansion against Constant Pressure
• If external pressure is constant throughout the
expansion Vf
w = − pex  dV = − pex(Vf − Vi ) = − pex∆V
Vi

Indicator diagram
For example, the piston may be pressed on
by the atmosphere, a chemical reaction
produces a gas in a container

The work done by a gas when it expands

against a constant external pressure is
equal to the shaded area
 Free Expansion

• Opposing force is zero  pex = 0  dw = 0  w = 0

• No work is done when a system expands freely.

• This occurs when a system expands into a vacuum
 Reversible Expansion

• Reversible change in thermodynamics is a change

that can be reversed by an infinitesimal
modification of a variable

• If pex = p Vf
w = −  pdV
Vi

• Example of reversibility
– Thermal equilibrium between the two
systems with the sample temperature
 Isothermal Reversible Expansion
• Isothermal reversible expansion of a perfect gas
• PV = nRT  p = nRT/V
Vf Vf
Vf
w = −  pdV = −nRT  (1 / V )dV = −nRT ln
Vi Vi
Vi

• The work done by a perfect gas when it expands

reversibly and isothermally is equal to the area under the
isotherm p = nRT/V.

• The work done during the irreversible expansion against

the same final pressure is equal to the rectangular area
shown slightly darker.

• The reversible work is greater than the irreversible work

Isothermal Reversible Expansion
Vf
w = − nRT ln
Vi
• Overall the internal energy is constant for the isothermal
expansion of a perfect gas
– Expansion: Vf > Vi & w < 0
– The system has done work on the surroundings
– Correspondingly the internal energy reduces due to the work
– There is a compensating influx of energy as heat (isothermal)
• More work is done for a given change of volume when the
temperature is increased
• The maximum work available from a system is obtained when
the change takes place reversibly (non of the pushing power is
wasted)
 Heat Transactions
• dU = dq + dw = dq + dwexp + dwe
– dwexp : expansion work
– dwe : non-expansion (extra or additional) work e.g. electrical work of
driving a current through a circuit

• At constant volume, expansion work is zero

– dwexp = -pdV = 0
– no additional work, dwe = 0
– Then, dU = dq

• internal energy change and heat transfer at constant

volume, ΔU = qV (measuring heat flow  internal energy
change)
– Subscript implies a change at constant volume
– measuring heat flow  internal energy change
 Heat Capacity
The heat capacity of a substance is the
quantity of heat required to change the
temperature of the substance by 1 degree

C = q/∆T

Air ~ 1 J/K
Water ~ 4.18 J/K
 Heat Capacity
A small amount of water absorbs (releases) a large quantity of
heat for a correspondingly small temperature rise (fall).

Water is a very useful cooling Water also takes a long time to

agent in the cooling systems of cool. Hot water bottles were
automobiles and other engines employed on cold winter nights.
 Calorimetry q = C∆T

• Calorímetry: study of heat transfer

during physical and chemical
processes

• Calorimeter: a device for measuring

energy transferred as heat e.g.
adiabátic bomb calorimeter

Constant-volume bomb calorimeter

The bomb is the central vessel, which is strong
enough to withstand high pressures. The calorimeter
(for which the heat capacity must be known) is the
entire assembly shown here. To ensure adiabaticity,
the calorimeter is immersed in a water bath (outer
bath) with a temperature continuously readjusted to
that the calorimeter at each stage of the combustion
 Calorimetry

The calorimeter constant (heat capacity of a calorimeter) may

be measured electrically by passing a constant current, I, from a
source of known potential difference, ∆φ, through a heater for a
know period of time, t, for then

q = I·t·∆φ
e.g.
I = 10 A, ∆φ = 12 V, t = 300 s, then q = 36 kJ (∵ 1 AVs = 1 CV = 1 J)
If the T increased by 5.5 K, then calorimeter constant, C = q/∆T =
36 kJ/5.5K = 6.5 kJ/K

C = q/∆T
or q = C∆T
 Extensive vs. Intensive

• Extensive properties : • Intensive properties:

a property that a property that is
depends on the amount independent of the
of substance in the amount of substance in
sample the sample

• ex) mass, volume, heat • ex) temperature,

capacity (100 g of pressure, mass
water has 100 times density, molar heat
the heat capacity of 1 capacity at constant
g of water) volume CV,m = CV/n
(specific heat
capacity)
 Heat Capacity

• Internal energy increases when its temperature is raised

• heat capacity at constant volume, CV = (∂U/∂T)V. Definition
• = slope of the tangent to the curve
• molar heat capacity, the heat capacity divided by the amount of substance,
Cm = C/n.
 Heat Capacity
dU = CV dT (at constant volume)

• In general, heat capacities depend on the temperature and

decrease at low temperatures

• However, over small ranges of temperature at and above

room temperature, the variation is quite small and for
approximate calculations heat capacities can be treated as
almost independent on the temperature

∆U = CV ∆T (at constant volume)

• If CV is constant over ∆T
 Heat Capacity
∆U = CV ∆T
∆U = qV (∵ w = 0 for non-expansion work & no additional work)
therefore, qV = CV ∆T

CV = qV /∆T

• Heat capacity (at constant volume) is the ratio of energy transferred

as heat to the temperature rise
• A large heat capacity implies that, for a given quantity of energy
transferred as heat, there will be only a small increase in temperature
• Infinite heat capacity means there will no increase in temperature (e.g. at
phase transition such as boiling of water)
 Enthalpy
• ∆U = qV (at constant ∆U = qV ∵ w = 0
volume) ∆U < qp ∵ w < 0
∆H = qp
• ∆U ≠ qV ( if the system is
free to change its volume)
• ∆U < q (some of the energy
supplied as heat to the system
is returned to the
surroundings as expansion
work
• ∆U < q p (at constant
pressure).
• ∆H = q p (the energy
supplied as heat at constant
pressure)
 Enthalpy
• Enthalpy, H = U + pV (definition)
• Enthalpy change and heat
transfer at constant pressure,
ΔH = qp.
• dH = dq (at constant pressure, no
additional work)
• Isobaric calorimeter, a calorimeter
for studying processes at constant
pressure.
 Enthalpy
H = U + pV (by definition)
H + dH = (U + dU) + (p + dp) (V + dV)
= U + dU + pV + pdV + Vdp + dpdV
= H + dU + pdV + Vdp (∵ dpdV ~ 0)

therefore, dH = dU + pdV + Vdp

dU = dq + dw
dH = dq + dw + pdV + Vdp
if there is only expansion work : dw = -pdV
dH = dq + Vdp
at constant pressure, dp = 0
dH = dqp (at constant pressure; no additional work)
Isobaric Calorimeter
 Enthalpy and Energy

• Relation between ΔU and ΔH,

• H = U + pV

• For the processes involving gases

• H = U + pV = U + nRT (perfect gas)
• ΔH = ΔU + ΔngRT.
• Δng (change in the amount of gas molecules in
the reaction)

• For solids and liquids

• ΔH ≈ ΔU (∵ very small change in volume 
negligible expansion work)
Heat Capacity at Constant Pressure
• Heat capacity at constant pressure,
Cp = (∂H/∂T)p .
dH = Cp dT (at constant pressure)
∆H = C p∆T (at constant pressure)
qp= Cp∆T

• when the temperature variation

needs to be considered
Cp,m = a + bT + c/T2 (a, b, & c are Cp is the slope of the tangent to a plot of enthalpy
empirical and independent of T against temperature at constant pressure
and can be found by fitting this
expression to experimental data)
 Relation Between Heat
Capacities
• Most systems expand when heated at
constant pressure (work done)
• The temperature rise is less than when
heating occurs at constant volume (larger
heat capacity)
• In most cases, Cp > Cv
• Cp - Cv = nR (perfect gas)  will be
discussed in Topic 2D
 Thermochemistry

• Study of the energy transferred as heat during

the course of chemical reactions

• Branch of thermodynamics

• System: reaction vessel + contents

• Chemical reaction results in energy exchange

between system and surroundings
 Thermochemistry

• Use calorimetry to measure the heat

qv = ∆U or qp = ∆H

• Exothermic reaction at constant pressure 

release energy by heating the surroundings (∆H <
0)

• Endothermic reaction  absorb energy by cooling

the surroundings (∆H >0)
 Standard Enthalpy Changes

• ΔH o : the change in enthalpy for a process in which the

initial and final substances are in their standard states
• Standard state of a substance at a specified temperature is
its pure form at 1 bar

• H2O(l)  H2O(g) ΔvapH o (373 K) = +40.66 kJ mol-1

• Standard enthalpies may be reported for any temperature
but
• Conventional temperature for reporting thermodynamic data
is 298.15 K (= 25.00 oC)
 Enthalpy:A State Function
• ΔsubH o = ΔfusH o + ΔvapH o
• Enthalpy is a state function: a change in enthalpy is independent of the
path between the two states
• Enthalpy changes of a forward process and its reverse differ in sign
• ΔH o(A B) = -ΔH o(B A)
 Lattice Enthalpy (ΔHL)
MX(s)  M+(g) + X-(g)

Solid is ionic & the strong Coulomic interaction

of the ions must be overcome

Lattice enthalpy is the change in standard molar

enthalpy for this process

Experimental value of the lattice enthalpy are

obtained by using a Born-Haber cycle, a closed
path of transformations starting and ending a
the same point

One step of which is the formation of the solid

compound from a gas of widely separated ions
 Born-Haber Cycle

1. Sublimation of K(s)
2. Dissociation of ½ Cl2(g)
3. Ionization of K(g)
4. Electron attachment to Cl(g)
5. Formation of solid from gas
6. Decomposition of compound
 Hess’s Law

• the standard enthalpy of an overall

reaction is the sum of the standard
enthalpies of the individual reactions into
which a reaction may be divided

1. C3H6 + H2  C3H8 -124 kJ/mol

2. C3H8 + 5O2  3 CO2 + 4H2O -2200 kJ/mol
3. H2O  H2 + 1/2O2 +286 kJ/mol
-----------------------------------------------------------------------
4. C3H6 + 9/2O2  3 CO2 + 3 H2O -2058 kJ/mol
 Enthalpies of Chemical Change
• Thermochemical Equation
– Chemical reaction + Corresponding change in standard enthalpy

– CH4(g) + 2O2(g)  CO2(g) + 2H2O(l) ΔH o = -890 kJ

– Pure, separate reactants in their standard states  Pure,

separate products in their standard states

• 2A+B3C+D
• ΔrHo = {3Hmo (C) + Hmo (D)} – {2Hmo (A) + Hmo (B)}
• Hmo (J) : standard molar enthalpy of species

• ΔrH o = ΣProducts vHmo – ΣReactants vHmo

However, absolute values of standard molar enthalpies are unknown

 Standard Enthalpies of
Formation
Standard enthalpy of formation (ΔfH o )
• standard reaction enthalpy for the formation of the compound
from its elements in their reference state
• reference state of an element is its most stable state at the
specified temperature and 1 bar.
• for example, at 298K
– The reference state of nitrogen is a gas of N2 molecules
– That of mercury is liquid mercury
– That of carbon is graphite
– That of tin is the white form

• 6 C (s, graphite) + 3 H2 (g)  C6H6 (l)

• +49 kJ/mol – 3(0) – 6(0) = 49kJ/mol
 Standard Enthalpies of
Formation
• standard enthalpies of formation of ions in solution poses a
special problem because it is impossible to prepare a solution
of cations alone or of anions alone
• Standard enthalpy of hydrogen ion is defined as zero at all
temperature

• ΔfH o (H+, aq) = 0

• If ΔfH o of HBr (aq) is found to be -122 kJ/mol then the
whole of that value is ascribed to the formation of Br - (aq)
• ΔfH o (Br -, aq) = -122 kJ/mol
• that value may then be combined with, for instance, the
enthalpy formation of AgBr(aq) to determine the value of
ΔfH o (Ag+, aq)
 The Reaction Enthalpy in Terms of
Enthalpies of Formation

Elements

Reactants
ΔrH o
Products

ΔrH o = ΣProducts v∆Hfo – ΣReactants v∆Hfo

Conceptually, we can regard a reaction as proceeding by

decomposing the reactants into their elements and then
forming those elements into the products.
 Temperature Dependence

• The temperature dependence of reaction enthalpies

• Kirchhoff’s law for the temperature dependence of

reaction enthalpies,
T 2

• ΔrH o(T2) = ΔrH o(T1) +  ∆ r C οp dT

T1

• The difference of the molar heat capacities of products and

reactants under standard conditions weighted by the
stoichiometric coefficient that appear in the chemical
equation
 Differential Scanning
Calorimetry
• A differential Scanning Calorimetry (DSC)
measures the energy transferred as heat to or
from a sample at constant pressure during a
physical or chemical change

– Differential: the behavior of the sample is compared to

that of a reference material (doesn’t undergo a physical
or chemical change)

– Scanning: the temperature is scanned or increased

– Calorimetry: calor means heat and metron means

measurement
Differential Scanning Calorimetry

Two small compartments are heated electrically at a constant rate

T = T0 + α t
T0 is initial temperature
α is the temperature scan rate
t is the time
Computer controls the electrical power supply that maintains the
sample temperature in the sample and reference compartments
throughout the analysis
Differential Scanning Calorimetry
• If no physical or chemical change occurs in the
sample at T,
• Heat transferred to the sample is qp = Cp∆T
– Where ∆T = α t

• Physical or chemical change requires excess heat

to maintain the same temperature change
– qp + qp,ex = (Cp+ Cp,ex) ∆T
– Cp,ex = qp,ex/∆T = qp,ex/ α t = Pex/ α
• Excess electrical power (Pex = qp,ex/t) necessary
to equalize the temperature of the sample and
reference compartments
Differential Scanning Calorimetry

A DSC trace (or thermogram): Cp,ex vs. T

Enthalpy change is equal to the area under the plot

 State & Path Functions

• Path 1: adiabatic
• Path 2: non-adiabatic
• Internal energy change depends on initial and final states
• dU exact differential
• Work and heat depend on the path
• dq inexact differential
 State & Path Functions
• State functions: depend on the current state of
the system and are independent of its previous
history - internal energy and enthalpy
• Path functions: processes that describe the
preparation of the state - work and heat

• Exact and inexact differentials

– exact differential: an infinitesimal quantity which, when
integrated, gives a result that is independent of the path
between the initial and final states. (dU)
– inexact differential: an infinitesimal quantity that, when
integrated, gives a result that depends on the path
between the initial and final states. (dq and dw)
 State & Path Functions

f f
∆U =  dU = Uf − Ui q= dq ≠ qf − qi
i i , path
Exact differential Inexact differential
Changes in Internal Energy
If both V & T change
infinitesimally

∂U ∂U
dU = ( )T dV + ( )V dT
∂V ∂T

πT, Internal pressure

CV, heat capacity

dU = πT dV + CV dT
 Joule Experiment
• Perfect Gas
∂U
π T = ( )T = 0
∂V

When there are no interactions between the molecules,

the internal energy is independent of their separation
and hence independent of the volume of the sample
Joule Experiement

• W = 0, no work was
done in the
expansion
• Q = 0, no change in
temperature was
measured (due to
large heat capacity
of the apparatus)
•  πT = 0
 ∆U at Constant Pressure
dU = πT dV + CV dT divide by dT 
∂U ∂V
( ) p = πT ( ) p + CV
∂T ∂T

Expansion coefficient Isothermal compressibility

1 ∂V 1 ∂V
α = ( )p κT = − ( )T
V ∂T V ∂p
Fractional volume change in Fractional volume change in response
response to the change of T to the change of p
 ∆U at Constant Pressure
∂U ∂V
( ) p = πT ( ) p + CV
∂T ∂T
1 ∂V 1 ∂V
α = ( )p κT = − ( )T
V ∂T V ∂p

∂U Perfect gas ∂U
) p = CV
( ) p = απTV + CV (
∂T
∂T πT = 0

Cv of a perfect gas is defined as the slope of a plot of

internal energy against T at constant V, Cv is also the
slope at constant p
Relation Between Cp and CV for a
perfect gas

∂H ∂U
Cp − CV = ( )p − ( )p
∂T ∂T
H = U + PV = U + nRT
∂U ∂U
Cp − CV = ( ) p + nR − ( ) p = nR
∂T ∂T
Cp − CV = nR
Cp , m − CV , m = R
 The Joule-Thomson Effect
the cooling of a gas by adiabatic expansion

at constant H

divide by dp

adiabatic
µ is Joule-Thomson Coefficient
Expansion at Constant Enthalpy

q = 0 implies ∆U = w
(adiabatic)
w1 = -pi(0-Vi) = piVi
w2= -pf(Vf-0) = -pfVf
w = w1+w2 = piVi – pfVf
Uf – Ui = w = piVi – pfVf
Uf + pfVf = Ui + piVi
or Hf = Hi

• Expansion occurs without

change of enthalpy
 Joule-Thomson Effect

µ T = (∂ H / ∂ p )T
µ T = − C pµ
Positive: cooling when expanding
Joule-Thomson Effect

µ T = (∂ H / ∂ p )T
µ T = − C pµ
Joule-Thomson Effect

Positive: cooling when expanding

Z < 1: attractive interactions are dominant
Principle of Linde Refrigerator

Liquefy gases using Joule-Thompson expansion

 Molecular Interpretation on
the Joule-Thomson Effect
• Mean kinetic energy of molecules in a gas is
proportional to the temperature

• Reducing the average speed of the molecules is

equivalent to cooling the gas

• If the speed of the molecules can be reduced to

the point that neighbors can capture each other
by their intermolecular attractions, then the
cooled gas will condense to a liquid
 Molecular Interpretation on
the Joule-Thomson Effect
• To slow the gas molecules, we move molecules
apart from each other by expanding the gas

• The molecules in a real gas attract each other

• The molecules struggle against the attraction of

their neighbors (like a ball thrown into air)

• Kinetic energy must be converted into potential

energy to reach greater separations

• The molecules travel more slowly as their

separation increases
 Adiabatic Changes
• Adiabatic vs isothermal process

• The temperature of a perfect gas falls

when it does work in an adiabatic
expansion
 Adiabatic Changes
(Reversible Adiabatic Expansion)

• Work is done but no heat enters (∵

adiabatic process)
• Internal energy decreases
• Temperature of the working gas also
decreases

• Molecular Interpretation
– Kinetic energy of the molecules decreases as
work is done
– The average speed of molecules decreases and
hence the T decreases
 Adiabatic Changes
(Reversible Adiabatic Expansion)

• The internal energy change can be expressed as the sum of two

steps
• First step: V changes while T is held constant  No change in U
• Second step, the T changes at constant V  change in U
• Therefore, ΔU = CV (Tf - Ti) = CV ΔT
 Adiabatic Changes
(Reversible Adiabatic Expansion)

• ΔU = q + w (q = 0 because it is adiabatic)
• Work of adiabatic change, ΔU = CVΔT = wad
• Mean kinetic energy (U) is proportional to the temperature
change

• Temperature change accompanying reversible adiabatic

expansion of a perfect gas, Tf = Ti(Vi/Vf)1/c, c = CV,m/R.

• Pressure change accompanying reversible adiabatic

expansion of a perfect gas, pfVfγ = piViγ
– Heat capacity ratio, γ = Cp,m/CV,m.
– pV γ = constant.

• Please study Justification 2E.1 & 2E.2

 Adiabatic Changes
(Reversible Adiabatic Expansion)

• The adiabatic falls more

steeply (p ∝1/Vγ) than the
corresponding isotherm (p
∝1/V) (∵ γ > 1)

• Physical reason for the

difference:
– In an isothermal expansion,
energy flows into the system
as heat and maintain the
temperature
– As a result the pressure
does not fall as much as in an
adiabatic expansion
 Adiabatic Changes
(Reversible Adiabatic Expansion)

• The adiabat is the p-V

curve for adiabatic change
• γ >1
• for example, for a
nonlinear polyatomic
molecules (or for a
monatomic perfect gas)
• ∆Um = 3RT (= 3RT/2 )
• CV,m = 3R (=3R/2)
• Cp,m – CV,m = R (section 2.11)
• γ = 4/3 (=5/3) > 1