First Law of Thermodynamics,

Heat Capacity, Latent Heat and Enthalpy

Stephen R. Addison
University of Central Arkansas

January 17, 2013

Outline

Introduction
Heat and Work

The First Law of Thermodynamics

Sign Conventions

Heat capacity and specific heat

Water and Calorimetry
Heat Capacities at Constant Volume and Pressure
Heat Capacities of an Ideal Gas
Ratio of Specific Heats

Latent heat and enthalpy

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Introduction

Introduction

In this lecture, we introduce the first law of thermodynamics and examine

sign conventions.

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Introduction

Heat and Work

Heat and Work

Heat is the spontaneous flow of energy from one object to another caused
by a difference in temperature. Work is defined as any other transfer of
energy into or out of the system. Examples of work are: pushing on a
piston, stirring a cup of coffee, passing current through a resistor, etc. In
each case the temperature will rise as the systems energy is increased. We
dont say that the system is being heated because the flow of energy is not
spontaneous.
Heat and work refer to energy in transit. While we can talk about how
much energy is in a system, talking about how much work is in a system is
meaningless.

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The First Law of Thermodynamics

The First Law of Thermodynamics

Let E be the internal energy of a system then

4E = (Energy input by Heating) + (Work done on system ).
This is called the first law of thermodynamics, clearly it is just a
restatement of the law of conservation of energy. We will use Q, and W
to denote large or finite changes.

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The First Law of Thermodynamics

Inexact Differentials

Well use
dQ, and
dW to denote infinitesimal changes. Thus we will write
4E = Q + W ,
or
dE =
dQ +
dW .
Where Q,
dQ are negative if heat leaves the system, W ,
dW are negative
if work is done by the system. Many authors write
dQ and
dW to denote
inexact differentials, and to emphasize that there is no function Q or W to
take the differential of. That is Q and W are not state functions.

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The First Law of Thermodynamics

When a system changes from state 1 to state 2, while 4E is determinate,

Q and W are path dependent.

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The First Law of Thermodynamics

Sign Conventions

Sign Conventions

There are other sign conventions in use. Many authors define

4E = Q W so that any work done by the system is positive. My advice
on this sign convention is the same as my advice on all other sign
conventions you should know which sign convention you are using and
you should use it consistently.

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Heat capacity and specific heat

Heat Capacity and Specific Heat

In this section we will explore the relationships between heat capacities

and specific heats, and internal energy.

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Heat capacity and specific heat

Water and Calorimetry

Water and Calorimetry

The amount of energy required to raise the temperature of one gram of

pure liquid water from 14.5o C to 15.5o C is one calorie. This is equivalent
to defining the heat capacity of one gram of water under these conditions
to be one calorie. In general the heat capacity of any object is the ratio of
heat absorbed to temperature increase.

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Heat capacity and specific heat

Water and Calorimetry

Heat Capacity

The heat capacity of an object is the energy transfer by heating per unit
temperature change. That is,
C=

Q
.
4T

In this expression, we will frequently put subscripts on C , Cp , or Cv for

instance, to denote the conditions under which the heat capacity has been
determined. While we will often use heat capacity, heat capacities are
similar to mass, that is their value depends on the material and on how
much of it there is.

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Heat capacity and specific heat

Water and Calorimetry

Specific Heat

If we are calculating properties of actual materials we prefer to use specific

heats. Specific heats are similar to density in that they depend only on
material. Specific heats are tabulated. When looking them up, be careful
that you choose the correct specific heat. As well as tabulating specific
heats at constant pressure and constant volume, specific heats are given as
heat capacity per unit mass, heat capacity per mole, or heat capacity per
particle. In other words, c = C /m, c = C /n, or c = C /N. In elementary
physics mass specific heats are commonly, while in chemistry molar
specific heats are common. Be careful!

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Heat capacity and specific heat

Water and Calorimetry

So using differentials, we could write:

C=

dQ

,
dT


1
dQ
cm =
,
m dT
or
cmol

1
=
n

 
dQ
.
dT

is used to denote an inexact differential. (By

Where, as usual, the d
an inexact differential we mean that there is no function to take the
differential of, instead the symbol is used to denote a small amount.)

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Heat capacity and specific heat

Heat Capacities at Constant Volume and Pressure

Heat Capacities at Constant Volume and Pressure

By combining the first law of thermodynamics with the definition of heat

capacity, we can develop general expressions for heat capacities at
constant volume and constant pressure. If we apply a pressure p to a
piston in a gas filled cylinder, the gas will be compressed, the work on on
the gas is then W = p4V . So Writing the first law in the form
Q
, we arrive at
4E = Q p4V , and inserting this into C = 4T
C=

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4E + p4V
.
4T

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Heat capacity and specific heat

Heat Capacities at Constant Volume and Pressure

We can now evaluate this at constant volume, and we arrive at



4E
Cv =
.
4T v
For an infinitesimal process we write this as
 
dQ
Cv =
dT v
or


Cv =

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E
T


.
v

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Heat capacity and specific heat

Heat Capacities at Constant Volume and Pressure

Similarly we can calculate the heat capacity at constant pressure. So the

heat capacity at constant pressure is given by






4E + p4V
E
V
Cp =
=
+p
.
4T
T p
T p
p

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Heat capacity and specific heat

Heat Capacities at Constant Volume and Pressure

If we examine the expressions for heat capacity, apart from the quantity
held constant, we see that the expression for Cp contains an extra term. It
isnt too difficult to figure out what is going on. Most materials expand
when they are heated. The additional term keeps track of the work done
on the rest of the universe as the system expands.

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Heat capacity and specific heat

Heat Capacities of an Ideal Gas

Heat Capacities of an Ideal Gas

For an ideal gas, we can write the average kinetic energy per particle as
1
3
mhv 2 i = kT .
2
2
This comes from combining our calculation that
1
p = hv 2 i
3
with
=

M
Nm
=
and pV = NkT
V
V

so that

1
pV = NkT = Nmhv 2 i or 3kT = mhv 2 i,
3
and the result follows. (Note, as promised I have shown that E = E (T )
for an ideal gas.)
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Heat capacity and specific heat

Heat Capacities of an Ideal Gas

Our result is true for a monatomic gas, for a diatomic gas the internal
energy is 52 NkT and for a polyatomic gas it is 62 NkT - this is because the
individual particles have more degrees of freedom and the average energy
per molecule is kT
2 per degree of freedom. We have to consider rotational
kinetic energy in diatomic and polyatomic molecules.

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Heat capacity and specific heat

Heat Capacities of an Ideal Gas

We now calculate Cv and Cp for N particles.



E
3
Cv =
= Nk
T v
2
To calculate Cp , we make use of the ideal gas law in the form pV = NkT .




E
V
Cp =
+p
T p
T p
So,
3

3
5
Cp = Nk + p
(NkT /p)p = Nk + Nk = Nk
2
T
2
2

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Heat capacity and specific heat

Heat Capacities of an Ideal Gas

Comparing the expressions for Cp and Cv , we see that we can write

Cp Cv = Nk.
So in terms of the ideal gas constant, R, we can write
Cp Cv = nR.
This is an interesting result.

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Heat capacity and specific heat

Heat Capacities of an Ideal Gas

We should note that Cp = 72 R in diatomic gases and Cp = 28 R. (The

relationship between Cp and Cv still holds in those cases.)

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Heat capacity and specific heat

Ratio of Specific Heats

The ratio of specific heats

The ratio of heat capacities at constant volume and pressure is equal to the
ratio of specific heats under the same conditions as the amount of material
is eliminated when we form the ratio. Thus we can write the ratio as
=

Cp
cp
= .
Cv
cv

The values of are then 5/3 (monatomic gas), 7/5 (diatomic gas) and
4/3 (polyatomic gas).

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Latent heat and enthalpy

Latent Heat and Enthalpy

We now explore the the relationship between latent heat and enthalpy.

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Latent heat and enthalpy

Latent Heat

It is possible to transfer energy by heating without increasing temperature

of a material. This happens during phase changes. In a phase change, the
heat capacity becomes infinite. The appropriate term to consider is now
latent heat. We want to know how much energy is transferred by heating
during phase changes.

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Latent heat and enthalpy

We can define the latent heat as

L=

Q
Q
= .
m
N

Some books like to use to use the latent heat per molecule, I prefer to use
the latent heat per unit mass. The reason isnt deep, latent heats per unit
mass are easier to find! The definitions that I have given for latent heat
are ambiguous. (In the same way that the definition for heat capacity was
ambiguous). By convention, we assume that latent heats are calculated
under conditions of constant pressure, and normally that that pressure is
one atmosphere. Constant pressure processes are common enough that we
introduce a new variable to simplify calculations under constant pressure
conditions. That quantity is enthalpy.

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Latent heat and enthalpy

Enthalpy

Enthalpy, H, is defined through

H = E + pV .
It is possible to use enthalpy to purge heat from our vocabulary. I wont
do that, because most people still use heat, and youll need to
communicate with others. Basically, the pV term in enthalpy keeps track
of expansion/compression related work for us.

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Latent heat and enthalpy

Starting from the first law in the form

dE =
dQ p4V
(Lets call this the first law for hydrostatic processes) and the definition




E
V
Cp =
+p
,
T p
T p
and inserting H, we can rewrite the expression for Cp in terms of enthalpy.

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Latent heat and enthalpy

Thus,

Cp =
or


Cp =

(H pV )
T

H
T


p
p


+p

V
T

V
T


+p


,
p

V
T


,
p

producing the result


Cp =

E
T


+p
p

V
T


=

H
T


.
p

This expression is often taken as the definition of Cp .

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Latent heat and enthalpy

Enthalpy and latent heat are simply related. The latent heat of
vaporization Lv is defined as the difference in enthalpy between a fixed
mass of vapor and the same mass of liquid. That is Lv = Hvap Hliq.
Similarly, the latent heat of fusion is given by Lf = Hliq Hsol , and the
latent heat of sublimations is given by Ls = Hvap Hsol . These enthalpy
differences are related through Ls = Lf + Lv . We shall explore these
relationships further when we study phase transitions and the
Clausius-Clapeyron equation later.

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