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10.1 Heat capacities


10.2 Work done by a gas
10 Thermodynamics of gases 10.3 First law of thermodynamics
10.4 Isothermal and adiabatic
changes

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Objectives Objectives
(a) define heat capacity, specific heat g) relates cp and cV to the degrees of
capacity and molar heat capacity freedom
(b) use the equations: Q = C , Q = mc , Q h) use the relationship = cp,m /cV,m to
= nCV.m and Q = nCp,m identify the types of molecules
(c) derive and use the equation for work
done by a gas, W = p dV i) describe the isothermal process of a gas
(d) State and apply the first law of j) use the equations pV = constant and
thermodynamics, Q = U + W TV 1 = constant for adiabatic changes
(e) deduce the relationship U = nC V,m T k) illustrate thermodynamics processes
from the first law of thermodynamics; with p V graphs
(f) derive and use the equation Cp,m CV,m = l) derive and use the expression for work
R 3 done in the thermodynamic process 4

10.1 Heat capacity 10.1 Heat capacity


The study of relationships involving heat, Since n = m/M, thus m = nM,
mechanical work, and other aspects of energy where M = molar mass, therefore
and energy transfer for the system.
Thermodynamic system is any collection of Q = nMc T and
objects that is convenient to regard as a unit, C = Mc and
and that may have the potential energy to Q = nC T, where C = molar specific heat
exchange energy with its surroundings. (molar heat capacity) and
From the equation of specific heat capacity, n = number of mole
Q = mc T, where c = specific heat capacity,
m = mass of the object,
Q = quantity of heat,
T = temperature difference. 5 6

10.1 Heat capacity 10.1 Heat capacity


Molar specific heat (molar heat capacity) Molar Specific Heat at Constant Pressure, CP
is defined as the amount of heat required - is defined as the amount of heat required to
to raise the temperature of 1 mole gas by 1 raise the temperature of 1 mole gas by 1 K or 1
C at constant pressure. Or ,
K or 1 C.
Or C = Q/n T, Q
CP and Cp Mc p
n T
The unit of molar specific heat is J K-1 mol-1
or J C-1 mol-1 - where , cp = specific heat capacity at constant
pressure, Cp =molar specific heat at constant
pressure.
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10.1 Heat capacity 10.1 Heat capacity
Molar Specific Heat at Constant Volume, CV Relationship between CP and CV . Consider a
is defined as the amount of heat required to PV graph as shown in figure.
raise the temperature of 1 mole gas by 1 K or 1
C at constant volume. Or
Q
CV
n T
and CV McV
where cV : specific heat capac ity at constant volume
CV : molar specific heat at constant volume
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10.1 Heat capacity 10.1 Heat capacity


1. In process AB : Isochoric process (constant 1. Thus the 1st law of thermodynamics becomes
volume), the work done is U AB QAB nCV TB TA
WAB 0 U AB nCV T

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10.1 Heat capacity 10.1 Heat capacity


In process AC : Isobaric process (constant Since TB=TC then
pressure), the work done is
WAC P VC VA P V U AB U AC
thus the 1st law of thermodynamics becomes
nCV T nCP T P V
U AC QAC WAC
P V nR T
where Q AC nC P T

QAC nCP T
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Ratio between CP and CV Conclusion


For 1 mole of an ideal gas, U AB (1)CV T For 1 mole of an ideal gas

and f f
U AB R TB T A R T
2 2
and thus Since CV=CP-R thus Therefore the
ratio between CP and CV is given by ,
f 2
CP
R f 2
2
CV f
R
f
2
where is dimensionless constant and always
greater than unity.
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10.1 Heat capacity 10.1 Heat capacity
Heat is an energy transfer between a system and When a glass of water is placed on a hot plate,
its surroundings that is the result of random energy will spontaneously leave the hot plate
motion in the surroundings. and cause the internal energy of the water to
increase.
Note the difference between a work process and
Heat will always flow spontaneously from the
a heat process. system at higher temperature to the system at
In the former, there must be organized motion lower temperature, but heat can be made to flow
in the surroundings, but in the latter, the energy in the opposite direction as well if work is done
transfer is a result of random motion in the in the process.
surroundings. For example, a refrigerator relies on work done
by its compressor to move heat from a cold
freezer into a warm kitchen.
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10.1 Heat capacity 10.1 Heat capacity


Heat is a term that is used all the time in Phrases like "as friction slowed the block, heat
everyday life. In this context, it's okay to talk was generated in the sliding surface" are not
about the "amount of heat in a hot object," but difficult to find.
in the classroom it is important that a teacher In fact, as the block slows, the organized motion
emphasize the precise meaning of this term. of the block does work on the sliding surface
A hot object may contain a lot of internal and increases its internal energy.
energy, but it does not contain heat.

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10.2 Work done by a gas


Signs Convention for Heat, Q and Work, W
Sign of Q :
Q = positive value Heat flow into the
system
10.2 Work done by a gas Q = negative value Heat flow out of the
system
Sign of W:
W = positive value Work done by the
system
W = negative value Work done on the
system
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10.2 Work done by a gas 10.2 Work done by a gas


Figures Consider the infinitesimal (small, thus Suppose that the cylinder has Initial
A
Gas
almost zero) work done by the gas (system) a cross sectional area, A and
dx
during the small expansion, dx in a cylinder the pressure exerted by the A
with a movable piston as shown in figure gas (system) at the piston Final F

below. face is P.
A
Initial Gas The work, dW done by the
gas is given by
dW Fdx cos
dx where 0
and F PA dW PAdx
A
Final F and Adx dV
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thus dW PdV 24
10.2 Work done by a gas 10.2 Work done by a gas
In a finite change of volume from V1 to V2, For an ideal gas
V2 nRT
dW
V1
PdV
A PV nRT then P thus
Initial Gas V
then V2 1 V2
W
V2
PdV dx W nRT dV W nRT lnV V1
V1 A
V1 V
where Final F

W : work done
W nRT ln V2 lnV1
P : gas pressure V2 Work done in the
W nRT ln ideal gas
V1 : initial volume V2 : final volume V1
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10.2 Work done by a gas P-V graph


For a change in volume at constant Figures below show the pressure, P against
pressure, P volume, V graph (P-V Diagram) where Area
under the graph = Work done
W P V W P V2 V1 P P

For a change in volume at constant P1 1 P2 2


volume, V W P V
W P V2 V1 0 P2 2 P1 1
W 0 W 0
the work done is Work done at constant 0 V1 V2 V 0 V2 V1 V
Pressure
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P-V graph
Area under the graph = Work done

10.3 First law of thermodynamics

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10.3 First law of thermodynamics 10.3 First law of thermodynamics


A generalisation of the principle of conservation U = Won + Qinto OR U = W + Q
of energy to include energy transfer through If Q U is positive if positive work is
heat as well as mechanical work. done on the system.
Energy can be neither created nor destroyed but If W
only transformed the system.
Heat processes and work processes account for The first law of thermodynamics:
all possible energy transfers to a system. It
Eint = Q + W, where
therefore follows from conservation of energy
that the total change in the internal energy of a Eint: Change in the internal energy of the system
system is the sum of the work done on the Q: Energy transferred by heat to the system
system and the heat transferred to the system. W: Work done on the system
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10.3 First law of thermodynamics 10.3 First law of thermodynamics
The first law of thermodynamics is a special case Some special cases:
of the law of conservation of energy that relates Isolated system:
the change in internal energy of a system to the one that does not interact with its
net transfer of energy by heat and work. surroundings.
Internal energy is a state variable (like P, V, and Since Q = W = 0, Eint = 0 and Eint, i = Eint, f.
T): its value is determined by the state of the
system, independent of the path. Cyclic process:
a process that starts and ends at the same
state.
Since Eint = 0, Q = -W

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Internal energy Internal energy


The change in internal energy of a system during
while it does work, W, the internal energy, U any thermodynamic process is independent of
changes by amount equal to Q path.
U = U2 U1 = Q W, where Example: the system goes from state 1 to state 2
U1 = initial internal energy as shown below.
U2 = final internal energy
Q = quantity of heat transferred
W = work done
For infinitesimal (almost zero) change in energy,
dU = dQ - dW
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Internal energy Internal energy


The internal energy depends only on
temperature of the system.
If the initial and final (state) temperature of the
system is the same, hence U = U2 U1 = 0
because f
U nRT
2
The change in internal energy also zero in cyclic
thermodynamic process (repeated process)
because the initial and final state of the system
is the same.
U1 2 U1 4 2 U1 3 2
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Internal energy
Ideal gas
U is a function only of temperature, not of P, V
separately.
U (ideal gas) = kinetic energy of molecules + 10.4 Isothermal and adiabiatic changes
internal rotational and vibrational energy. This is
independent of the volume.
Place an ideal gas in a container of volume V.
Suddenly double the volume (open a valve to a
2nd container), kinetic energy of gas does not
change, the gas does no work.
Temperature does not change, U is unchanged. 39 40
10.4 Isothermal and adiabiatic changes Isothermal change
Four specific kinds of thermodynamic Isothermal Process
processes: is defined as a process that occurs at
Isothermal process: constant constant temperature i.e. U =0, thus U =
temperature Q W = 0; Q = W
Adiabatic process: No heat enters/leaves Then V
Q W nRT ln 2
a system (gas) V1
Isochoric (Isometric) process: constant 1V1 =P2V2, then
volume P1
V2 P1 therefore Q W nRT ln
Isobaric process: constant pressure V1 P2 P2
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Isothermal change Adiabiatic change


Note that: Definition is defined as a process that occurs
without heat transfer into or out of a system i.e.
If the gas expand isothermally,
thus U = Q W and U = U2 U1 = W
thus V2>V1 W = positive value
For Adiabatic expansion (V2>V1 ), W =
If the gas compress isothermally, positive value but
thus V2<V1 W = negative value U =negative value hence the internal
energy of the system decrease.
For Adiabatic compression (V2<V1 ), W =
negative value but
U =positive value hence the internal
energy of the system increase.
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Adiabiatic change Adiabiatic change


Example: the compression stroke in an internal Isochoric Process
combustion engine is an approximately Definition is defined as a process that occurs at
adiabatic process. constant volume, and W = 0 (no work done)
thus U=Q W and U = U2 U1 = Q
In an isochoric process, all the energy added as
heat remains in the system as an increase in
internal energy (because the temperature of the
system increase).
Example: heating a gas in a closed constant
volume container.
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Adiabiatic change Pressure-Volume Diagram (graph)


Isobaric Process The figure
Definition is defined as a process that occurs at shows a PV
constant pressure i.e. W = P V = P(V2 V1) thus diagram for
U = Q W and U = Q P(V2 V1) each
Example: boiling water at constant pressure. thermodyna
mic process
for a
constant
amount of
an ideal gas

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Adiabiatic change Adiabiatic change
Consider the 1st law of thermodynamics, written nRT
in differential (infinitesimal, approaching zero) nCV dT dV 0 dT CP dV
V 1 0
form : dU = dQ dW where dU = nCvdT RT T CV V
Then nCvdT + PdV = dQ and dQ = 0 CV dT dV CP
V and
Because adiabatic process. CV
Thus nCvdT + PdV = 0 dT R dV
0 dT dV
From the equation of state for an ideal gas, T CV V 1 0
PV = nRT then P = nRT/V
T V
Therefore nCvdT + (nRT/V)dV = 0 where R CP CV

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Adiabiatic change Adiabiatic change


For finite changes in temperature and volume, Note that:
integrate dT 1
dV
0 Adiabatic expansion (dV>0) always occurs
T V with a drop in temperature (dT<0).
dT dV
1 0
Hence T V Adiabatic compression (dV<0) always occurs
ln T 1 ln V constant with a rise in temperature (dT>0).
ln T ln V 1
constant Rearrange the equation of state for an ideal gas :
PV PV
ln TV 1
constant T thus V 1 constant
nR nR
1
TV constant
and T1V1 1
T2V2 1 PV constant or P1V1 P2V2
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Adiabiatic change Adiabiatic change


Work Done in Adiabatic Process P1V1 P2V2
Hence W nCV
In adiabatic process, Q=0 nR nR
hence the 1st law of thermodynamics becomes
CV
W P1V1 P2V2 and R C P CV
U = -W and U = nCv T R
CV
W = -nCv T W P1V1 P2V2
CP CV
W = -nCv(T2 T1)
W CP CV CV P1V1 P2V2
W = nCv(T1 T2) CP
P1V1 CP
Use equation of state, thus T1 W 1 P1V1 P2V2 but
nR CV CV
P2V2 1
T2 W P1V1 P2V2
and nR 1
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Summary
Thermodynamics of Gases

Heat capacities First Law of Work done


Cv,m = dU/dT
Cp,m - Cv,m = R
thermodynamic
Q = U +W
= p dV
= area under p-V
End of Chapter
= Cp,m / Cv,m graph
Internal energy
U = nCv,m T

Isothermal process Adiabatic process


T = constant Q=0
p1V2 = p2V2 = constant pV = constant
TV -1 = constant
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