Chapter 2

The First Law

 Thermodynamics
What is thermodynamics?
 “The study of the transformation of energy”
 Thermo – heat, dynamics – patterns of change
 Deals with conversion of energy
 Deals with direction of energy change
 Developed mostly in the 19th century (1800’s) after the general
acceptance of Dalton’s atomic theory (1808) but before the
development of quantum mechanics which implies that the
microscopic universe of atoms and electrons follow different rules
than the macroscopic rules of large masses.
 Deals mostly with the “bulk” properties of large collections
(ensembles) of atoms and molecules.
 Macroscopic rules for the transfer of energy.
Applications of Thermodynamics

Applications:
 Initially developed from observations of
scientists and engineers trying to develop
more efficient steam engines.
 Heating and cooling
 Refrigeration
 Development of new types of batteries
 Engine efficiency
 Energy transfer in biological systems
 Protein folding and molecular stability
Basic Concepts
 System
 The region of space that we are interested
in studying.
 Surroundings
 The region outside of the system from
which we make our observations.
 Universe
 System + surroundings
Types of Systems Depends on the characteristic of the
boundary which separates the system from
the surroundings

Open System : Allows matter and

energy to pass between the
system and surroundings.

Closed System : Allows energy, but

not matter, to pass between the
system and surroundings.

Isolated System : Neither matter nor

energy can pass between the system
and surroundings.
 Work (w)
The movement of an object a distance (s) against
an opposing force by means of an applied force (F).
 Mathematically, it is the dot product of
the distance vector with the applied
force vector:  
w  F  s  F s cos 
where θ is the angle between the
vectors.

The transfer of energy involving

organized motion. When work is
performed by a system on the
surroundings, the molecules in the
surroundings experience an orderly
motion. When work is done on a
system, molecules in the surroundings
are used to transfer energy in an
organized way to the system.
Problem 1:
Calculate the work needed for a 65 kg person to
climb through 4.0 m on the surface
a.The earth
b.The moon (g = 1.6 m/s2)

Problem 2:

A chemical reaction takes place in the container of cross-

sectional area 100 cm2. As a results of the reaction a
piston is pushed out through 10 cm against external
pressure of 1.0 atm.
Calculate the work done by system.
Heat (q)

 Energy transferred between the

system and its surroundings as a
result of a temperature
gradient.

 Involves random motion

(thermal motion) of molecules.
Heat Boundaries
Types of Boundaries
Diathermic Adiabatic
Allows for the transfer Does not allow the
of heat between transfer of heat
the system and between the system
surroundings if and surroundings.
there is a
temperature
gradient.
Heat Transfer Processes
 Exothermic Process
 Process that releases energy as heat.
 In a diathermic system, increases temperature
of surroundings.
 In an adiabatic system, increases temperature of
system.

 Endothermic Process
 Process that absorbs energy as heat.
 In a diathermic system, decreases temperature
of the surroundings.
 In an adiabatic system, decreases temperature
of system.
Internal Energy
 Internal Energy (U)
 The total energy of a system, including both
the kinetic and potential energy of the
molecules in the system.
 Does not include the kinetic energy arising
from the motion of the system as a whole,
such as its kinetic energy as it accompanies
the Earth on its orbit around the Sun.
 Is an extensive property – a property that
depends on the amount of matter (number of
moles). The more molecules, the greater
the internal energy.
 Units of Energy
Internal Energy, Work, and Heat are related
 Energy is the capacity to do work.
 Work is the way to transfer that energy between the system and surroundings through the
organized motion of matter.
 Heat is the way to transfer that e
 nergy between the system and surroundings through the disorderly motion of matter.
 All have the same units – the Joule (J).
1 J  1 kg m 2 s -2
Other units of internal energy, work, and heat:

Electronvolt (eV) Calorie (cal)

The amount of kinetic energy acquired The amount of energy required to
by an electron that is accelerated across raise the temperature of 1 gram of
a potential difference of 1 V. water by 1 C.

1 eV = 1.60218×10-19 J 1
 Changes in Internal Energy
 Change in Internal Energy (U)

 The change in internal energy as a system goes from an

initial state with an internal energy Ui to a final state with
an internal energy Uf.

U  U f  U i
 The internal energy of a system may be increased by:
 Doing work (w ) on the system.
 Transferring energy as heat (q ) to the system.
 Heat and work are equivalent ways of changing the
internal energy of a system.

 If a system is isolated from its surroundings, then no change

in internal energy takes place:

U  0
First Law of Thermodynamics
 First Law of Thermodynamics
 “For an isolated system, the total energy (internal
energy) remains constant.”
 Law of Conservation of Energy.
 The total energy of a system can ONLY be changed by
an organized transfer (work) or disorderly transfer
(heat) of energy between the system and surroundings.
 Mathematically,

U 
q – energy transferred as heat to the system.
w – work done on the system.
Sign of q and w are from the standpoint of the system.
If positive, system acquires energy. If negative, system
releases energy.
ΔU for Isolated Systems
 In an Isolated System
 No matter can be transferred between the system and
surroundings.
 No energy can be transferred (by work or heat)
between the system and surroundings.
 Thus, q = 0 and w = 0, and

U 
U  0
ΔU for Closed Systems
 In an Closed System
 No matter can be transferred between the
system and surroundings.
 Energy can be transferred (by work or heat)
between the system and surroundings.

U 
 If q > 0 and w > 0, heat and work are
transferred to the system.
 If q < 0 and w < 0, energy is lost from the
system as heat and work.
ΔU for Adiabatic Systems
 In an Adiabatic System
 Heat can not be transferred between the
system and surroundings.
 q=0
 Thus,
U  q  w
U  0  w
U  w
First Law of Thermodynamics
 First Law of
Thermodynamics
 “The work needed to change
an adiabatic system (q = 0)
from one specified state (Ui )
to another specified state (Uf
) is the same however the
work is done.”
 The change in internal
energy (ΔU) can be
determined by measuring the
work (wad) needed to bring
about a change in an
adiabatic system.
wad  U f 
 State and Path Functions
 State function
 Properties that are independent of how
a state is prepared.
 Functions of variables that define the
current state of a system, such as
pressure, temperature, and volume.
 Internal energy (U) is a state function.

 Path function
 Properties that relate to the path or
preparation of a state.
 The work (w) done in preparing the state
and the energy transferred as heat (q)
are path functions.
 Since systems do not possess work or
heat, but perform or transfer them, they
are not properties of the current state of
the system, but refer to the path taken
by the system in attaining the current
state.
 The work is different if the change takes
place adiabatically or nonadiabatically.
Exact Differentials
 An infinitesimal change in the internal energy of a system is
represented as the differential, dU.
 For a complete process, dU is integrated from the initial to
the final conditions.
 Mathematically,

 dU  U
 When dU is integrated, the result is the change in internal
energy for the process.
 dU is an exact differential because its integrated value of
ΔU is path-independent.U  U  U f i

 All state function have exact differentials.

Inexact Differentials
 Infinitesimal changes in the work or heat of a system are
represented as the differentials, dw and dq.
 For a complete process, dw and dq are integrated from the
initial to the final conditions.
 Mathematically,
wf qf

w 
wi , path
q 
dw 
qi , path
dq

 When dw and dq are integrated, the result is the absolute

amount of work and heat for the process.
 The differentials dw and dq are called inexact differentials
because their integrated values w and q are path-dependent.

w  wf  w
qi  q f  qi
Infinitesimal Changes
 For an infinitesimal change in the system:

dU  dq 
 Integration from initial to final conditions
gives:

 dU   dq
U 
 Which is the mathematical expression for
the First Law of Thermodynamics.
Expansion Work
 Expansion work
 Work arising from a change in volume,
including compression.

 In classical mechanics, the total work (w)

necessary to move an object a displacement
of (dz) against an opposing force (F) is:

w    Fdz
 Negative sign denotes that the system doing
the work will have a decrease in internal
energy.
 Expansion Work
 Considering the mechanical work performed
by an expanding gas confined in a
frictionless, massless, rigid, perfectly-
fitting piston:
F
w       A  dz
 A

w    pext dV
 A is the area of the cross section of the
piston.
 pext is the external pressure against
which the piston moves.
 dV is the infinitesimal change in volume
of the piston during the course of
expansion.
 Expansion Work
 If the external pressure (pext) is
constant, we can integrate
from an initial volume (Vi) to a
final volume (Vf):
Vf

w   pext  dV
Vi

w   pext V

where
V  V f  Vi
 Free Expansion
 If there is no external pressure (pext), or opposing
force, the system experiences a free expansion.
 Occurs when a gas expands into a vacuum, a region of
space with no pressure.
 Because pext = 0 for a free expansion, the work (w)
performed by the system is: V
f

w   pext  dV
Vi
Vf

w    0   dV
Vi

w0
Reversible Expansion
 Reversible Process –
 A process during which the system is never more than infinitesimally
far from equilibrium (mechanical and thermal).
 During a reversible process, the system remains at equilibrium with
the surroundings at all times.
 An infinitesimal change in the external conditions of the surroundings
causes an infinitesimal change in the system.
 The infinitesimal change in the system can be reversed by an
infinitesimal return to the external conditions of the surroundings.
 In reality, reversible processes can not be achieved because it would
take an infinite amount of time to carry out a series of infinitesimal
changes. A reversible process is an idealization.

 Irreversible Process –
 A process which cannot be reversed by an infinitesimal
change in the external conditions.
 During an irreversible process, the system makes a finite
departure from equilibrium.
 All real processes are irreversible processes.
 Reversible Expansion
 Reversible Expansion –
A expansion in infinitesimally small steps so that the system remains at
mechanical equilibrium with the surroundings during the course of the
expansion.
In this case, the internal pressure of the piston (p) equals the external
pressure (pext) of the surroundings during the course of the expansion:
p  pext
The work of reversible expansion (wrev) is:
Vf

wrev   
Vi
pext dV

Vf

  
Vi
pdV

Because the external pressure is not constant throughout the course of the
expansion, it cannot be brought outside of the integral.
Isothermal Reversible Expansion
 Isothermal Reversible Expansion –
 A reversible expansion performed at constant
temperature in which the system is in contact with a
constant thermal surroundings.

 For a reversible expansion of a perfect gas in a

piston:
 The work of reversible expansion (wrev) is:

Vf

wrev    pdV
Vi

 The pressure is related to the volume by:

nRT
p
V
Isothermal Reversible Expansion
 The reversible expansion work (wrev) is:
Vf
 nRT 
wrev     dV
Vi 
V 

 Because the gas is confined and the temperature is

constant, n and T are constants,
Vf and the work is:
1 
wrev   nRT V  V  dV

i

wrev   nRT (ln V f  ln Vi

 Evaluating the integral gives:
 Vf 
wrev   nRT ln  
 Vi 
Isothermal Reversible Expansion
 The reversible expansion work (wrev) of a perfect gas is:

 Vf 
wrev   nRT ln  
 Vi 

 During an expansion (when vf > vi), wrev < 0, meaning that

the system has performed work on the surroundings and
the internal energy of the system has decreased.

 Because the process is at constant temperature, there is

a compensating influx of energy as heat, so overall the
internal energy is constant.

 Also, more work is done for a given change in volume at

higher temperatures.
Isothermal Reversible Expansion
 Consider an indicator diagram that compares a
reversible isothermal expansion to an irreversible
expansion against a constant external pressure.
 More work is obtained for a reversible expansion
than for an irreversible expansion.
 Matching the external pressure to the internal
pressure at each state of the process ensures that
none of the “pushing power” is wasted.
 If pext > p, compression occurs, and there is a
decrease in the amount of work done.
 If p > pext , the “pushing power” is wasted.
 Represents the maximum available work for a
system between specific initial and final states
and for a specific path.
 Using Boyle’s Law, the work for isothermal
reversible expansion in terms of pressures:

 pi 
wrev  nRT ln  
p 
 f 
Problem 3
Heat
Transactions
 The First Law of Thermodynamics may also be expressed as –

dU  dq  dwexp  dwe
 dq – infinitesimal change in heat energy transferred across a diathermic boundary.
 dwexp – infinitesimal amount of energy as work due to gas expansion.
 dwe – additional work (such as electrical work of driving a current through a circuit).

 If no additional work is applied, dwe= 0.

 If the gas is confined to a vessel of constant volume (rigid walls), the gas cannot expand and
cannot perform any expansion work, dwexp = 0.
 In this case:

Subscript
dU  dq
V denotes a constant-volume condition.
For a measurable finite change: V

If qv > 0, heat is applied to the system.

If U  qV
qv < 0, system loses heat to surroundings.
 Calorimetry
Calorimetry – the study of heat transfer during physical and chemical
processes.
Calorimeter – a device for measuring the heat transferred.
Specific heat capacity (s)
 The amount of heat required to raise the temperature of one
gram of a substance by one degree Kelvin (or Celsius).
 Intensive property of the material composing the system.
 Materials with a low specific heat, such as many metals,
need little heat for a relatively large change in temperature.
Heat capacity (C)
 The amount of heat required to raise the temperature of a
given quantity of the substance by one degree Kelvin (or

C 
Celsius).
 Extensive property, depends on the amount of material.
 The relationship between the heat capacity and the specific
heat capacity of a substance is:
where m is the
mass of the
substance in
grams.
Calorimeter instrument
Heat and Heat Capacity
 Theamount of heat (q) that has been absorbed or
released by a particular substance undergoing a
change in temperature (ΔT) is:

q  C T
where (C) is the heat capacity of the substance.
Adiabatic Bomb Calorimetry
 The absolute internal energy (U)
of a system cannot be measured
directly.
 “No work or heat meters.”

 However, the change in internal

energy (ΔU) due to the transfer
of heat may be measured by an
adiabatic bomb calorimeter.
 Adiabatic – no heat transfer
between the system and
surroundings.
 Bomb – a sturdy vessel (usually
very thick stainless steel) that
maintains a constant volume
and withstands very high
pressure.
 Used to study combustion
reactions and explosions.
Adiabatic Bomb Calorimetry
 How does it work?
1. A known mass of a sample is
placed inside the “bomb” and the
bomb is pressurized with O2 with
a high pressure (~30 atm).
2. The bomb is immersed in a
stirred water bath. The
combined device is the
calorimeter (system).
3. The calorimeter is also immersed
in an outer water bath
(surroundings). The temperature
of both the outer and inner water
bath are monitored and adjusted
to the same temperature during
the course of the combustion
reaction. As a result, there is no
heat transfer between the
calorimeter and outer water
baths, and the process is
adiabatic.
Adiabatic Bomb Calorimetry
 How does it work?
The heat (qV) released or absorbed is proportional to the change in
temperature (ΔT). Thus, a measurable ΔT causes a measurable
ΔU:
U  qV  CV 
The proportionality constant (CV), calorimeter constant, is the
constant-volume heat capacity of the calorimeter.
– Unique to each calorimeter (bomb + inner bath).
– Must be determined by calibrating the calorimeter by
either:
• Measured electrically by passing a current (I) from a source of
known potential (V) through a heater for a period of time (t).

q  IVt
• By burning a known mass of standard substance (benzoic acid),
that has a known heat output.
Heat Capacity and Internal Energy
 Increasing the temperature
increases the internal energy (U) of
the system.
 The slope of the tangent to the
curve is defined as the heat
capacity at constant volume.
 Formally defined, the heat
capacity at constant volume is:
 U 
CV   
 T V

 This is a partial derivative, which is

a slope with all variables except
one held constant.
Heat Capacity and Internal Energy
 The internal energy (U) of the system
actually varies with volume and
temperature.
 The heat capacity at constant volume ( C )
V
varies with both volume and temperature.
 Temperature-dependence of heat capacity:
 Heat capacity decreases with lower
temperature.
 Over small temperature changes above 298
K, variations in the heat capacity are
small, and it can be considered to be
temperature-independent. In this case:

dU  CV dT
 If the heat capacity is independent of
temperature over the range of
temperatures of interest, a measurable ΔT
causes a measurable ΔU a measurable in a
constant-volume system:

U  qV  CV 
Heat Capacity and Internal Energy
 For a fixed quantity of heat:

U  qV  CV T
 A large heat capacity implies that there will be only a small
increase in temperature, and the sample has a large capacity for
heat.
 An infinite heat capacity implies that there will be no increase
the system’s temperature no matter how much heat is supplied
to the system.
 At a phase transition (melting or boiling point), the temperature
does not rise as heat is supplied. Thus, at the temperature of a
phase transition, the heat capacity of a sample is infinite.
 Molar heat capacity at constant volume, (CV, m)
 heat capacity per mole of material.
 an intensive property.
Enthalpy

 For a system that is not at constant volume, ΔU is not equal to

the heat supplied, as for a fixed-volume system.
 Under these circumstances, some of the energy supplied as heat
to the system causes the gas to expand, performing expansion
work on the surroundings. As a result, dU <dq .
 The enthalpy ,H, is defined as:

H U 
where U, p, and V are the internal energy, pressure, and volume
of the system, respectively. Since these parameters are all state
functions, the enthalpy is also a state function.
 An infinitesimal change in enthalpy (dH) is related to
infinitesimal changes in the internal energy (dU), pressure (dp) ,
and volume (dV) of the system by:

dH  dU  d ( pV )
 Enthalpy
 Applying the Product Rule for the differentiation of two
functions:

dH  dU
 From the First Law,

dU  dq  dw
 The infinitesimal change in enthalpy (dH) becomes:

dH  dq
 If the system is at constant pressure, or isobaric condition, then
dp = 0, the infinitesimal change in enthalpy (dH) :

dH  dq 
Enthalpy

 The infinitesimal change in enthalpy (dH) for

a system at constant pressure is:

dH  dq  d
 Moreover, if the system is at mechanical
equilibrium with the surroundings at constant
pressure p , then only expansion work is
being done:
dw   pdV
 The infinitesimal change in enthalpy (dH)
becomes:
dH  dq p
Enthalpy
 The enthalpy change (ΔH ) for a measurable amount of
heat at constant pressure:

H  q p
 An enthalpy change can be measured calorimetrically by
monitoring the temperature change that accompanies a
physical or chemical change occurring at constant
pressure.

 Isobaric calorimeter – a calorimeter that maintains a

constant pressure.

 Two types of isobaric calorimeters:

 Adiabatic flame calorimeter
 Differential scanning calorimeter
Enthalpy Change for a Perfect Gas
 The enthalpy of a perfect gas is related to its internal
energy by:

H U 
H  U 
 This implies that the measurable change in enthalpy in a
reaction that produces or consumes gas at constant
temperature is:

H  U  RT ng
 where Δng is the change in the number of moles of gas during
the reaction.
Enthalpy Change for a Perfect Gas
 Consider the combustion of hydrogen gas to form wate r:

2H2 (g) + O 2 (g)  2H2O (l)

 Three moles of gas are replaced with two moles of liquid.

 So Δng = 0 – 3 = -3 moles. At 298 K,

H  U  RT ng
 J 
 (3 mole)  8.314  (298 K)
 mole K 
 7.5 kJ
 Why is the difference negative?
 Heat escapes from the system during the reaction (ΔH < 0), but the
system contracts as the liquid is formed. Energy is returned to the
system from the surroundings in the form of work, increasing the
internal energy (ΔU > 0).
 Temperature Dependence of Enthalpy
 The enthalpy (H) of a substance increases
as the temperature increases.
 The relation between the increase in
enthalpy and the increase in temperature
depends on the condition of constant
pressure:
 Consider the plot of enthalpy versus
temperature at constant pressure:
 The slope of the tangent to the curve
is defined as the heat capacity at
constant pressure (Cp), and is an
extensive property.
 Formally defined, the heat capacity at constant
pressure is:
 H 
Cp   
 T  p
 The molar heat capacity at constant pressure
(Cp,m) is an intensive property and is the heat
capacity per mole of material.
Temperature Dependence of Enthalpy
 The heat capacity at constant pressure (Cp) is used to relate the change
in enthalpy to a change in temperature.
 For an infinitesimal change in temperature, dT, the corresponding
infinitesimal change in enthalpy (dH) at constant pressure is:
dH  C p dT
 For a measurable change in temperature, ΔT, the measurable change in
enthalpy (ΔH ) at constant pressure is:
H  q p  C p T
 The molar heat capacity at constant pressure (Cp,m) varies with
temperature.
 The variation can be ignored under a small temperature range.
 Under larger temperature ranges, a convenient approximate
empirical expression is:
c
C p ,m  a  bT  2
T
 where the coefficients a, b, and c are independent of temperature
and unique for each substance.
Relationship between Cp and CV
For a given increase in temperature, the enthalpy
(H) of a system will increase more than the internal
energy (U).
At constant pressure, most systems expand when
heated, and do work on the surroundings, decreasing
the internal energy (U). Thus, some of the energy
supplied as heat is returned to the surroundings as
work.
As a result, the temperature of the system rises
less than when the heating occurs at constant
volume.
This implies that the constant-pressure heat
capacity is larger than the constant-volume heat
capacity:

C p  CV
For a perfect gas, the relationship between the two
heat capacities is:

C p  CV  nR
 Adiabatic Changes
 An adiabatic change occurs when the system is isolated
from the surroundings and heat (q) is not allowed to
pass between them.
 For an adiabatic process, dq = 0.
 From the First Law of Thermodynamics:

dU  dq 
 Since dq = 0, the infinitesimal change in internal energy
(dU) is:
dU ad  dwad
where the subscript denotes an adiabatic process.
 For an adiabatic process, work is completely converted
into internal energy.
 Adiabatic Changes
If an ideal gas in a system is allowed to expand
adiabatically, the temperature of the gas
decreases.
Why?
 As the system does work on the
surroundings, it has a decrease in the
internal energy.
 There is less kinetic energy for molecular
motion, so the average molecular speeds
decrease, and the temperature decreases.
The adiabatic “two-step”:
The volume changes while the temperature is fixed
at the initial temperature (Ti). There is no change
in the internal energy if the gas is a perfect gas.
The temperature of the gas is reduced at
constant volume or a perfect gas. The
change in internal energy results only
from this step, if CV is independent of
temperature.
 Adiabatic Changes
 The internal energy (U) is a function of the volume (V)
and temperature (T) of the gas: U (V, T)
 Assuming that the gas is in a closed system with n constant.
 If the volume and temperature of the gas is known, the
pressure can be determined from an Equation of State
(Ideal Gas Equation, van der Waals equation, etc.)
 Volume and temperature are independent variables.
 The total differential (dU), which relates the
infinitesimal change in internal energy to infinitesimal
changes in the temperature (dT) and volume (dV) is:
 U   U 
dU    dT    dV
 T V  V T
Adiabatic Changes

 The heat capacity at constant volume, CV, is defined as:

 U 
CV   
 T V
 The infinitesimal change in internal energy (dU) is;

 U 
dU  CV dT    dV
 V T
 For an ideal gas:

 U 
  0
 V T
 And the infinitesimal change in internal energy (dU) is:

dU  CV dT
 Adiabatic Changes
 For an adiabatic expansion of an ideal gas, dq = 0, and:

dU ad  dwad
 Integrating both sides gives:
Tf

wad  C
Ti
V dT

 During an adiabatic process, the pressure, volume, and

temperature of the gas changes.
 For an ideal gas expanding adiabatically and performing
reversible work (where the external and internal pressures are
always matched) in a piston: Vf

wad    pdV
Vi
 Adiabatic Changes
 Equating these expressions for the adiabatic, reversible work of
an ideal gas:
Tf Vf


Ti
CV dT   
Vi
pdV

 Since the gas in an ideal gas:

Tf Vf
nRT
C
Ti
V dT   
Vi
V
dV

T Vf
 Isolating the variables of integration:
f
CV nR

Ti
T
dT   
Vi
V
dV
 Adiabatic Changes
 Integrating, taking CV to be independent of temperature:
 Tf   Vf 
CV ln     nR ln  
 Ti   Vi 
 Simplifying:
CV  T f   Vf 
ln     ln  
nR  Ti   Vi 

CV  T f   Vi 
ln    ln  
nR  Ti  V
 f 

 Which may be rearranged to give: CV

Vi  T f  nR
 
V f  Ti 
 Adiabatic Changes
 The expression:
CV
Vi  T f  nR
 
V f  Ti 

may be rearranged to: CV

Tf  Vf  nR
 
Ti  Vi 

 This variation of temperature as a

perfect gas is expanded reversibly and
adiabatically is shown for different
values of CV/nR:
 For gases with a low heat capacity, the
decrease in temperature faster.
 Adiabatic Changes
 Since the final and initial states of an ideal gas must satisfy the ideal
gas equation:

piVi p fVf
 nR 
Ti Tf
which may be rearranged to:

p fVf Tf

piVi Ti
 For an adiabatic, reversible expansion of an ideal gas from an initial
state to a final state, the volume and temperature are related by:
CV
Vi  T f  nR
 
 Substituting gives: V f  Ti 
CV
Vi  p f V f  nR
 
V f  piVi 
 Adiabatic Changes
 Simplifying:
CV CV
Vi  p f   V f 
nR nR
   
V f  pi   Vi 
CV CV
 p f   Vf   Vf 
nR nR
1      
 pi   Vi   Vi 
CV CV
1
 pi  nR
 Vf  nR
   
 pf   Vi 
CV CV  nR
 pi  nR
 Vf  nR
   
 pf   Vi 
 From the relationship:
C p  CV  n
 Adiabatic Changes
 Substituting gives: CV Cp
 pi  nR
 V f  nR
   
 pf   Vi 
nR
 CV
Raising both sides to the power:
CV nR C p nR
 
 pi  nR CV
 Vf  nR CV
   
 pf   Vi 

Cp

pi  V f  CV
 Finally gives:  
p f  Vi 
Heat Capacity Ratio and Adiabats
 The heat capacity ratio of a substance is defined as:

Cp

CV
 Thus, the pressure and volume relationship for an ideal gas
undergoing reversible, adiabatic expansion is:


pi  V f 
 
p f  Vi 
 Which can be expressed as:

piVi   p f V f

pV K
where K is a constant.
 Heat Capacity Ratio and Adiabats
 Because Cp >CV , .


 1
Adiabat – A graphical relation
between pressure and volume for
adiabatic changes.
 For an adiabat:

1
p 
V
 For an isotherm:
1
p
V

 Thus, the pressure declines more

steeply for an adiabat than for a
corresponding isotherm because of
the temperature decrease.
 Automotive Adiabats
 In order to carry out a process adiabatically,
the system must be thermally isolated from
the surroundings by insulating material.

 However, there are many processes around us

that come close to being adiabatic without
thermal barriers.

 For example, expansion and compression in an

automobile engine are adiabatic processes
because the change takes place so fast (0.1 to
0.01 seconds) that there is not enough time
for heat to cross the boundary.
 Thermochemistry
 Thermochemistry –
 The study of heat produced or required by
chemical reactions.
 Branch of thermodynamics because a reaction
vessel and its contents form a system, and
chemical reactions result in the exchange of
energy between the system and the surroundings.

 The heat (q) produced or absorbed by a chemical

reaction is equal to:
 ΔU if a chemical reaction occurs at constant volume.
 ΔH if a chemical reaction occurs at constant pressure.
 Thermochemistry
 In thermochemistry, chemical reactions are classified as:
 Exothermic
 A process in which heat is released from the reacting system to the
surroundings.
 The temperature of the system is higher immediately after the
reaction than initially; heat must be transferred from the system to
the surroundings to return the system to its initial temperature.
 The heat of the reaction, qrxn < 0, because the system is losing
energy as heat.
 At constant pressure conditions, ΔH < 0.
 Endothermic
 A process in which heat is absorbed by the reacting system from
the surroundings.
 The temperature of the system is lower immediately after the
reaction than initially; heat must be transferred from the
surroundings to the system to return the system to its initial
temperature.
 The heat of the reaction, qrxn > 0, because the system is gaining
energy as heat.
 At constant pressure conditions, ΔH > 0.
 Standard Enthalpy Changes
 The standard enthalpy change (ΔHo) – the change in
enthalpy for a process in which the initial (pure,
unmixed reactants) and final (pure, separated
products) substances are in their standard states.
 Standard state – the pure form of a substance at a
specified temperature and at 1 bar of pressure.
 Standard enthalpy of transition (ΔtrsHo) – the standard
enthalpy change that accompanies a change of physical
state at 1 bar.
 Standard enthalpy of vaporization (ΔvapHo) – the
standard enthalpy change per mole when a pure liquid
at 1 bar vaporizes to a gas at 1 bar.
 Standard enthalpy of fusion (ΔfusHo) – the standard
enthalpy change that accompanies the conversion of a
solid to a liquid at 1 bar.
 Enthalpy as a State Function
 Enthalpy is a state function and
independent of path between the two
states.
 ΔHo is the same however the change is
brought about provided that the initial
and final states are the same.
 Consider the sublimation, or the
conversion of a solid directly to a gas, of
water:
fusion: H2O(s) → H2O(l) ΔfusHo
vaporization: H2O(l) → H2O(g) ΔvapHo
sublimation: H2O(s) → H2O(g) ΔsubHo
 sub H o
  fu
 Enthalpy as a State Function
 Since enthalpy is a state function,
the enthalpy change for a forward
process and that for its reverse
process differ only in sign.

H  A  B   H  B  A
o o

 Consider the condensation, or the

conversion of a gas directly to a liquid,
of water:
condensation: H2O(g) → H2O(l)
ΔconHo
 vap
vaporization: H
H O(l) → H O(g)   con H
2
o
2
Δ Ho
 Enthalpy of Chemical Change
 Standard Reaction Enthalpy (ΔrHo )
 The enthalpy change for a reaction per mole of
reactant at a specified temperature.

 
 The standard reaction enthalpy may beo determined
from the standard molar enthalpies H m of products
and reactants:
r H o
 
products
vH

 where v is the stoichiometric coefficient of the

reactant or product from the balanced chemical
reaction.
 Enthalpy of Chemical Change
 Standard Enthalpy of Combustion (ΔcHo )
 The standard reaction enthalpy for the complete oxidation of an organic
compound to carbon dioxide gas and liquid water as well as to nitrogen gas, if
the compound contains a nitrogen atom.
 Example, the combustion of propane:

CH3CH2CH3 (g) + 5O2 (g)  3CO2 (g) + 4H2O(l) ;  cHo  2200 kJ m

 Hess’s Law
 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.
 Based on the path-independence of enthalpy.
 Allows for the reaction enthalpy for a reaction which may be difficult to
measure directly to be determined from information on other reactions.
 Application of Hess’s Law
 Calculate the standard enthalpy of combustion of
propene:
9
CH2 =CHCH3 (g) + O2 (g)  3CO2 (g
5

Given the following thermodynamic data:

CH2 =CHCH3 (g) + H2 (g)  CH3CH2CH3 (g) ;  r Ho  124 kJ mol-1

CH3CH2CH3 (g) + 5O2 (g)  3CO2 (g) + 4H2O(l) ;  cHo  2200 kJ mol-1
1
H2O(l)  H2 (g) + O 2 (g) ;  r Ho  286 kJ
2

______________________________________
9
CH2 =CHCH3 (g) + O 2 (g)  3CO 2 (g) + 3H2O(l) ;  cH  2058 kJ mol-1
o

5
 Standard Enthalpy of
 Formation
Standard Enthalpy of Formation
 The standard reaction enthalpy for the formation of a compound
from the elements in their reference state, which is the most
stable state of the element at the specified temperature and at
1 bar of pressure.
 The standard enthalpies of formation of elements in their
reference states are zero at all temperatures.
 The standard reaction enthalpy may be determined from the
standard enthalpies of formation of reactants and products from
the relation:

r H o
 
products
v

 where v is the stoichiometric coefficient of the reactant or

product from the balanced chemical reaction.
Temperature Dependence
of

Reaction Enthalpy
The enthalpy of a reaction (ΔrH) is temperature
dependent.
 Sometimes it is necessary to determine the
enthalpy at a temperature from which there is no
tabulated data.
 When a substance is heated from T1 to T2 , its
enthalpy changes from H(T1) to H(T2):
T2

H (T2 )  H (T1 )   C p dT
T1

 This relationship assumes that there is no phase

change that takes place in the temperature range
of interest because the heat capacity is infinite at a
phase transition.
Temperature Dependence
of Reaction

Enthalpy
Kirchhoff’s Law - The standard reaction
enthalpy change from ΔrHo(T1) to ΔrHo(T2) is:

T2

 r H o (T2 )   r H o (T1 )   r p dT
 o
C
T1
 The  C ois the difference between the
molar heat
r p capacities of products and
reactants under standard conditions
weighted by the stoichiometric
coefficients:

 r C po  
products
vC po , m  
reactants
vC po , m
 The can normally be assumed to be
independent of temperature over
 r C p limited temperature ranges.
reasonably
o
References
• Peter Atkins and Julio de Paula, Physical
Chemistry, 7th edition, W. H. Freeman and
Company, 2002.
• Dr. Robert W. Schurko, University of Windsor,
Ontario, Canada.
http://mutuslab.cs.uwindsor.ca/schurko/