Department of Atmospheric Sciences

ATM 404/504 Thermodynamics

Ch. 4

st 1

Law of Thermodynamics

Heat Capacities
o Consider a homogeneous system of constant composition o Write dU (dH) as a total differential of the independent variables X and Y (for our purposes, X and Y could be any pair of p, V, and T). Then dU = ( U X )Y dX + ( U Y )X dY o From the 1st Law, Q = dU + pdV, we can substitute to get dV dQ = ( U T )V dT + p + U V ( ) T where X and Y are T and V, respectively.

Department of Atmospheric Sciences

ATM 404/504 Thermodynamics

Ch. 4

st 1

Law of Thermodynamics

Heat Capacities
o From Q = dH Vdp we can substitute for dH to get dp dQ = ( H T )p dT + H p V ( ) T where X and Y are T and p, respectively. o For a process of heating at V = const we get cv m = Cv = dQ dT = ( U T )V or per unit mass we can write cv = dq dT = ( u T )v

Department of Atmospheric Sciences

ATM 404/504 Thermodynamics

Ch. 4

st 1

Law of Thermodynamics

Heat Capacities
o For a process of heating at p = const we get c p m = C p = dQ dT = ( H T )p or per unit mass we can write c p = dq dT = ( h T )p o Can also calculate heat of change of V and p at T = const

dQ dV = ( U V )T + p, and dQ dp = ( H p )T - V o Not very useful, but given for completeness

Department of Atmospheric Sciences

ATM 404/504 Thermodynamics

Ch. 4

st 1

Law of Thermodynamics

Calculation of Internal Energy and Enthalpy

o Our equations for CV and Cp can be integrated directly for processes with V = const and p = const, respectively to find U and H, if CV and Cp are known as functions of T

U=

C dT + const and H = C dT + const

v p

o CV and Cp, from experiment, are usually polynomials in T

C = a + b T + gT 2 + K

Department of Atmospheric Sciences

ATM 404/504 Thermodynamics

Ch. 4

st 1

Law of Thermodynamics

Calculation of Internal Energy and Enthalpy

o Consider 2 rigid vessels linked by a connection with a stopcock (pg. 34). One contains gas, the other evacuated. o Stopcock opened, gas in 1 expands to occupy both vessels. o Temperature measurements show that system exchanges no heat with environment no work done, Q = 0, W = 0, and U = 0. o Since p changed during process, we have U = U(T) only and partial derivative used above are total derivatives.

Department of Atmospheric Sciences

ATM 404/504 Thermodynamics

Ch. 4

st 1

Law of Thermodynamics

Calculation of Internal Energy and Enthalpy

o Notes on this experiment
When experiment done carefully, small heat exchange was found (Joule-Thomson effect), which vanishes for ideal gas behavior As gas confined in vessel 1 expands into 2, work is done by some portions of gas against others while volumes change (as molecules enter 2, they are effected by molecules following) These are internal transfers that are not included in W This shows the importance of defining system carefully and clearly when considering a thermodynamic process In this case, the system is all the gas contained in both vessels (initially one is empty), whose total volume (V1 + V2) does not change

Department of Atmospheric Sciences

ATM 404/504 Thermodynamics

Ch. 4

st 1

Law of Thermodynamics

More on Heat Capacities

o As noted above, since U = U(T) we have CV = dU/dT and cv = du/dT o We can write H = U + pV = U + nR*T = H(T) leading to Cp = dH/dT and cp = dh/dT

o Since we are only interested in differences in internal energy and enthalpy, we can set the integration constant to 0 giving: U CVT, H CpT, u cvT, and h cpT

Department of Atmospheric Sciences

ATM 404/504 Thermodynamics

Ch. 4

st 1

Law of Thermodynamics

More on Heat Capacities

o Since we have CV = dU/dT, Cp = dH/dT and H = U + pV = U + nR*T, we have dH dT = dU dT + nR* C p = CV + nR*

leading to Cp CV = nR* cp cv = R recalling that

n = m/M.

o As mentioned earlier, heat capacities for all gases can be measured and the coefficients for the polynomial expansion can be determined (C = + T + T2 + )

Department of Atmospheric Sciences

ATM 404/504 Thermodynamics

Ch. 4

st 1

Law of Thermodynamics

More on Heat Capacities

o For simple gases like N2, O2, and Ar, the experimental data are nearly constant for all temperatures and pressures of interest, so the temperature variation is not considered. o From earlier we have, for monatomic gases, the total internal energy is U = (3/2)NkT, which leads to CV = (3/2)nR* and cv = (3/2)R. Similarly, Cp = (5/2)nR* and cp = (5/2)R. o For diatomic gases, where there are more degrees of freedom, so we get CV = (5/2)nR* and cv = (5/2)R. Similarly, Cp = (7/2)nR* and cp = (7/2)R. The ratios Cp/CV = cp/cv = .

Department of Atmospheric Sciences

ATM 404/504 Thermodynamics

Ch. 4

st 1

Law of Thermodynamics

More on Heat Capacities

o Dry air is considered to be a diatomic gas, so the second form applies. o The ratio, cp/cv = = 1.4. o We then attach the subscript, d, to the specific heats to indicate dry air. o This leads to cvd = 718 J kg-1 K-1 and cpd = 1005 J kg-1 K-1 and Rd = cpd cvd = 287(.05) J kg-1 K-1.

Department of Atmospheric Sciences

ATM 404/504 Thermodynamics

Ch. 4 1st Law of Thermodynamics

More on Heat Capacities
o The table below shows the values of cpd for various temperatures and pressures. Note the slight variation.

Department of Atmospheric Sciences

ATM 404/504 Thermodynamics

Ch. 4

st 1

Law of Thermodynamics

More Forms of the 1st Law

o Using the above expressions for (specific) heat capacities, we get more useful forms of the 1st Law, two of which are particularly useful dQ = Cv dT + pdV , and dq = cv dT + pd a and dQ = C p dT - Vdp, and dq = c p dT - a dp

Department of Atmospheric Sciences

ATM 404/504 Thermodynamics

Ch. 4

st 1

Law of Thermodynamics

Special Cases
o For an isothermal transformation Q = nR*T ln V f Vi o For an isochoric (constant volume) transformation D U = Q = CV (T f - Ti ) o For an isobaric transformation Q = C p (T f - Ti ) and W = p (V f - Vi )

D U = C p (T f - Ti )- p (V f - Vi )