Basic Concepts of Thermodynamics

Thermodynamics is the study of transformations of energy

System and surroundings
the system is the part of the world in which we have a special
interest. A system has definite boundaries
the surroundings is everything outside the boundaries
Classification of systems:
An open system can exchange matter as well as energy with its
surroundings
a closed system can exchange energy with its surroundings. No
transfer of matter across the boundaries is possible
an isolated system can exchange neither energy nor matter with
its surroundings

Chapter 2 1
 Work, Heat, and Energy

The energy of a system is a measure of its capacity to do work

The energy of a system is the sum of the kinetic and potential
energies of all particles in the system
The energy of a closed system can be changed by:
work done on or by the system
heat transfer across its boundaries
Work is transfer of energy using organized motion (expansion
work, electrical work, etc.)
Heat is transfer of energy using thermal motion (chaotic,
random motion of molecules)

Chapter 2 2
 Heat Transfer

The boundary of a system is diathermic if heat can be

transferred between system and surroundings
The boundary of a system is adiabatic if heat cannot be
transferred.
Adiabatic processes (no heat transfer between system and
surroundings) take place in adiabatic systems
A process that releases energy as heat is called exothermic
A process that absorbs energy as heat is called endothermic

Chapter 2 3
 Internal Energy

The internal energy, U, is the total energy of a system

We cannot give an absolute value of U but we can calculate U
for a process
U = Uf - Ui
Uf = final value of U
Ui = initial value of U
U is a state function (the value of U depends only on the current
state of the system)
U is an extensive property

Chapter 2 4
 The First Law

U = q + w for a closed system

q = heat supplied to or removed from the system (q <0 if heat
removed from system)
w = work done on or by the system (w <0 if work done by the
system)
q and w depend on the process by which the state is changed;
they are not state functions
U = 0 for an isolated system
the internal energy of an isolated system is constant
dU = dq + dw ( the First Law written for infinitesimal
changes)

Chapter 2 5
 Expansion Work

dw = - pexdv
dw is the expansion work (pressure-volume work) when a system
undergoes a change
pex is the external pressure
dV is the change in volume
dw <0 (work is done by the system) when system expands (dV>0)
w = - pexdV
integration from Vi to Vf when volume changes from Vi to Vf

Chapter 2 6
 Expansion Work, cont

Free Expansion - no opposing force

pex = 0 (expansion into a vacuum)
w=0
Expansion against Constant Pressure
pex is constant
w = - pexV (V is the volume change)
Isothermal Reversible Expansion of Perfect Gas
pex = p (reversible expansion)
p = nRT/V (ideal gas)
w = - nRT dV/V
w = - nRT ln(Vf/Vi)

Chapter 2 7
 Reversible Process

A process is regarded as thermodynamically reversible if it can

be caused to go in either direction by an infinitesimal change
in an external variable such as pressure or temperature
Reversible changes occur when a system is in equilibrium with
its surroundings
For a reversible expansion: p = pex + dp
dp 0
p = pex
w = - p dV

Chapter 2 8
 Indicator Diagram or PV-diagram

The expansion work, w, can be obtained from an indicator

diagram (a plot of p versus V)
The amount of work done by the gas is given by area under
curve
The maximum work available for a system operating between
specified initial and final states is obtained when the change
takes place reversibly ( pex = p)

Chapter 2 9
 U for Process at Constant Volume

dU = dq + dw
dw = dwexp + dwe
wexp is expansion work (pressure-volume work)
we is other work (electrical work etc.)
dwexp = 0 for a process taking place at constant volume
dU = dq (if no electrical work)
dU = dqv (subscript v indicates process at constant volume)
U = qv for process at constant volume

Chapter 2 10
 Calorimetric Determination of U

An adiabatic bomb calorimeter (a constant volume calorimeter)

is used to determine U
The change in temperature, T, of the calorimeter upon
reaction is proportional to U or qv
qv = C T
C is the heat capacity of the calorimeter
C can be determined by electrical calibration
Electrical work is given by: w = IVt or w = I2Rt
I = current
V = voltage over heater
R = resistance of heater
t = heating time

Chapter 2 11
 Heat Capacity at Constant Volume

CV = (U/T)V
CV is the heat capacity at constant volume
(U/T)V is a partial derivative which shows how U varies
with T when the volume is kept constant
CV,m = CV/n
CV,m is the molar heat capacity at constant volume

Chapter 2 12
 Change in U with T

dU = CV dT at constant volume
from definition of CV
U = CV T at constant volume
assuming that CV is independent of T
U = qv at constant volume
qv = CV T
qv is heat needed to change temperature by T

Chapter 2 13
 Enthalpy, H

H = U + pV (Definition of enthalpy)
H is a state function (U, p, and V are all state functions)
H is an extensive property
H = qp for a process taking place at constant pressure
assuming pressure-volume work is the only type of work involved in
the process

Chapter 2 14
 Heat Capacity at Constant Pressure

Cp = (H/T)p
Cp is the heat capacity at constant pressure
Cp shows the variation of H with T at constant pressure
Cp,m = Cp/n
Cp,m is the molar heat capacity at constant pressure
dH = Cp dT at constant pressure
H = Cp T at constant pressure
assuming Cp is independent of T
H for chemical reactions can be determined using a calorimeter
operating at constant pressure

Chapter 2 15
 Relation between H and U

H = U + pV
H = U + (pV) for a process (change)
(pV) is small for processes involving condensed phases (solids and
liquids) only
(pV) is generally significant for processes involving gases
H U for processed involving condensed phases only
(pV) = (nRT) for a gas (ideal gas)
H = U + (ngasRT) for processes involving gases

Chapter 2 16
 Change in Temperature of Gas

(ngasRT) = ngasR T
for a change in temperature of a given amount of gas
H = U + ngasR T
relation between the change in enthalpy and internal energy of a
given amount of gas when the gas is heated or cooled

Chapter 2 17
 Relation between H and U for a Reaction
Involving Gases

aA(g) + bB(g) cC(g) + dD(g)

reaction is assumed to take place at constant temperature
ngas = (c + d) - (a + b)
ngas is the change in number of moles of gas upon reaction
(ngasRT) = RT ngas
H = U + RT ngas
relation between the enthalpy change and the change in internal
energy for a reaction taking place at constant temperature

Chapter 2 18
 Adiabatic Changes

q = 0 for adiabatic changes

no heat transfer
The following is true for adiabatic compression (reduction of
volume of system in an adiabatic change:
work is done on the system
the internal energy of the system increases
the temperature of the system increases
ln (Tf/Ti)c = ln (Vi/Vf) for reversible and adiabatic compression of
an ideal gas
c = CV/nR

Chapter 2 19
 Thermochemistry

Exothermic reactions release heat

H < 0 for an exothermic reaction taking place at constant pressure
The standard state of a substance at a specified temperature is its
pure form at 1 bar pressure
The standard enthalpy change, H, is the change in enthalpy for
a process in which the initial and final substances are in their
standard states

Chapter 2 20
 Enthalpies of Phase Transitions

Standard Enthalpy of Vaporization, vapH

vaporization: A(l) A(g)
vapH is the enthalpy change when 1 mol of pure liquid A at 1 bar
vaporizes to give 1 mol of pure gaseous A at 1 bar pressure
vaporization is an endothermic process
Standard Enthalpy of Fusion, fusH
fusion or melting: A(s) A(l)
Enthalpies (heats) of fusion are positive (endothermic processes)
Standard Enthalpy of Sublimation, subH
sublimation: A(s) A(g)
sublimation processes are endothermic

Chapter 2 21
 Thermochemical Laws

The enthalpy change for a forward process and its reverse must be
equal in magnitude but opposite in sign
H(AB) = -H(BA) for the process A B
If the overall reaction is composed of several individual steps, then
the enthalpy change of the overall reaction is given by the sum of
the enthalpy changes of the individual steps (Hesss Law)
H = H(step1) + H(step2) + ..
subH = fusH + vapH

Chapter 2 22
 Enthalpies of Chemical Change

The standard reaction enthalpy , rH, is the change in enthalpy

when products and reactants are in their standard states
The standard enthalpy (heat) of combustion, cH, is the standard
reaction enthalpy for the complete oxidation of an organic
compound
the products are CO2 and H2O if compound contains C, H, and O
N2 is also formed if compound contains N
heats of combustion values are listed in Table 2.5

Chapter 2 23
 Standard Enthalpies of Formation

The standard enthalpy of formation , fH, of a substance is the

s6tandard enthalpy for its formation from its elements in their
standard states (most stable state at 1 bar pressure
fH = 0 for an element in its standard state
The standard reaction enthalpy is given by the sum of the
enthalpies of formation of the products minus the sum of the
standard enthalpies of formation of the reactants
aA + bB cC + dD
rH = cfH(C) + dfH(D) - (afH(A) + bfH(B))

Chapter 2 24
 Temperature Dependence of Reaction Enthalpies

dH = Cp dT at constant pressure
H(T2) H(T1) = Cp dT
Integration from T1 to T2
H(T2) - H(T1) = Cp dT (Kirchhoffs Law)
Integration from T1 to T2
H(T2) is the enthalpy change of reaction at temp. T2
H(T1) is the enthalpy change of reaction at temp. T1
Cp = Cp(products) - Cp(reactants)

Chapter 2 25