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the derrivatives from Cp and Cv in thermodynamic

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References: An Introduction to Atmospheric Thermodynamics, Tsonis

Introduction to Theoretical Meteorology, Hess

Physical Chemistry (4th edition), Levine

Thermodynamics and an Introduction to Thermostatistics, Callen

ENTHALPY

U and V are not the only state variables that we can use to characterize a

thermodynamic system. We can choose other variables that can be related to U

and V, such as T, p, or S.

One commonly used state variable is called enthalpy, and is defined as

H U + pV.

The differential of H is given as dH = dU + pdV + Vdp. This makes it possible to

write the first law of thermodynamics as

dH = dQ + Vdp .

(1)

The reason enthalpy is convenient to use is that for constant pressure processes,

dp = 0 and so dH = dQ.

Since many thermodynamic processes in the atmosphere occur at constant

pressure, change in enthalpy and heat are equivalent and are used

interchangeably in such processes.

From the first form of the first law, dU = dQ pdV, we see that at constant

volume, dU = dQ.

For constant volume processes, heat and change in internal energy are

interchangeable.

It is worth repeating the following:

For constant pressure processes, heat and enthalpy change are equivalent.

For constant volume processes, heat and internal energy change are

equivalent.

process,

dW = dU dH ,

which states that the work is the difference in the changes of internal energy

and enthalpy.

Heat capacity refers to the amount of heat required to raise the temperature of a

substance by one degree. Heat capacity is defined in terms of either a constant

volume process or a constant pressure process,

Q

Cv

T v

(2)

Q

Cp

.

T p

(3)

From the two forms of the first law we can show that

Q U

T v T v

Q H

T p T p

so that the definitions for heat capacity can also be written as

U

Cv

T v

(4)

H

Cp

.

T p

(5)

Heat capacity is an extensive property. Its intensive counterpart is called

specific heat, and is defined as

cv

cp

Cv u

=

m T v

(6)

h

=

.

m T p

(7)

Cp

Heat capacities and specific heats are not constant, but are functions of T and p.

RELATION BETWEEN Cv AND Cp

To see the relation between Cv and Cp we start with the relation

H U

C p Cv =

.

T p T v

(8)

H = U + pV ,

H

U

V

=

+ p

.

T p T p

T p

(9)

U

V U

C p Cv =

+ p

.

T p

T p T v

(10)

The differential of U is

U

U

dU =

dT +

dV .

T V

V T

Dividing by dT gives

dU U U dV

=

.

+

dT T V V T dT

and assuming constant pressure we get

dU U U dV

+

dT p T V V T dT p

or

U

U

U V

=

+

.

T p T V V T T p

(11)

U

V

C p C v =

+ p

V T

T p .

(12)

u

c p cv =

+ p

.

T

T p

( U

(13)

For gases, Cp is greater than Cv. This is because in a constant pressure process

some of the heat added will be used to do work as the system expands, so the

internal energy cannot increase as much as in a constant volume process.

Recall that the specific heat at constant volume was defined as

u

cv

T v

And the specific heat at constant pressure was defined as

h

cp

T p

Since the internal energy and enthalpy of an ideal gas depend only on

temperature, then for an ideal gas we dont have to write the specific heats as

partial derivatives, but can instead use full derivatives

du

dT

.

dh

cp

dT

cv

From the expressions for the internal energy of ideal gases, we then get that

3

R ; monatomic gas

2

5

cv = R ; diatomic gas

2

cv =

The expression relating the specific heats at constant pressure and at constant

volume is also greatly simplified for an ideal gas. The general expression

[Eqn. (13)] becomes, for an ideal gas,

c p cv = R ,

(14)

5

R ; monatomic gas

2

7

c p = R ; diatomic gas

2

cp =

99% of the atmosphere is composed of diatomic molecules (N2 and O2), and has

a specific gas constant of 287.1 J-kg1-K1. This leads to values of cv and cp of

718 J-kg1-K1 and 1005 J-kg1-K1. These values are extremely close to the

measured values for the atmosphere.

The specific heats for ideal gasses are

du

dT

.

dh

cp =

dT

cv =

du = cv dT

dh = c p dT

following two forms for the first law

cv dT = dq pd

c p dT = dq + dp

We are often most interested in how the thermodynamic variables change with

time. By dividing the first law by dt we get

dT dq

d

=

p

dt dt

dt

dT dq

dp

cp

=

+

dt dt

dt

cv

In meteorology, the most common form of the first law used the top equation

above. There are many different symbols used for the heating term. Some

common ways that you will see the first law written in other textbooks are

DT

dQ

=

Dt

dt

DT

D

cv

+p

=J

Dt

Dt

dT

Dp

= H

cp

dt

Dt

Cp

Bluestein, (1992)

Holton, (1992)

Houze, (1993) .

BEWARE: Not all textbooks use consistent notation. Many (such as Bluestein)

use upper case C for specific heat.

The first law is often referred to as the thermodynamic equation or

thermodynamic energy equation.

EXERCISES

1. Show that for an ideal gas

u

c p cv =

+ p

T

T p

reduces to

c p cv = R .

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