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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
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QAC nCP T
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and f f
U AB R TB T A R T
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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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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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P-V graph
Area under the graph = Work done
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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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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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Summary
Thermodynamics of Gases