Chapter 2: Work, Heat, and Energy:

The First Law of Thermodynamics

PRINCIPAL FACTS AND IDEAS
1. Thermodynamics is based on empirical laws.
2. The first law of thermodynamics asserts that the internal energy U is a
state function if: ΔU = q + w
where q is an amount of heat transferred to the system and w is an amount
of work done on the system.
3. Heat is one way of transferring energy.
4. Work is another way of transferring energy.
5. The first law of thermodynamics provides the means to calculate amounts
of work and heat transferred in various processes, including adiabatic
processes.
6. The enthalpy is a state function whose change in a constant-pressure
process is equal to the amount of heat transferred to the system in the
process.
7. The enthalpy change of a chemical reaction can be calculated from the
enthalpy changes of formation of all products and reactants.
2.1. Work and the State of a System
Thermodynamics involves work and heat.
Mechanical Work
The amount of work done on an object equals
the force exerted on it times the distance it is
moved in the direction of the force. If a force Fz
is exerted on an object in the z direction, the
work done on the object in an infinitesimal
displacement dz in the z direction is
where dw is the quantity of work. The SI unit of
force is the newton (N = kgms−2), and the SI unit
of work is the joule (J = kgm2 s−2 = Nm).

If the force and the displacement are not in the

same direction, they must be treated as vectors.
The formula in Eq. (2.1-2) can be written in
terms of Cartesian components as:
For a finite process we can divide the
displacement into small steps such that the
force is nearly constant in each step. The work
done on the object in the entire process is
obtained by adding the work done in all of the
steps. If the displacement and force are both in
the z direction this integral is:
The Work Done on a Closed Fluid System
If a force is transmitted
between a system and
its surroundings and if
the volume of the system
changes there is work done
by the surroundings on the
system or by the system on
the surroundings. If the height of the piston, z,
increases by an infinitesimal amount dz, the amount of
work done on the surroundings is given by Eq. (2.1-1):

where F(transmitted) is the force that is actually

transmitted to the surroundings.
Reversible Processes
At equilibrium, the force exerted on the piston
by the gas is equal to

where P is the pressure of the gas and A is the

area of the [Link] define the external
pressure Pext by

At equilibrium
For an infinitesimal step of a reversible
process the work done on the
surroundings is given by

where V is the volume of the system.

Work done on the system:

The signs we have used correspond to the

following convention: A positive value of w or
dw corresponds to work being done on the
system by the surroundings. A negative value of
work of dw corresponds to work being done on
the surroundings by the system.
This kind of work is sometimes called
compression work or PV work. A gas is a
simple system.
Work Done on an Ideal Gas in a Reversible Process
For a finite reversible change in volume of n moles of an
ideal gas,

If the temperature is constant the process is called

isothermal. For an isothermal process,

where V1 is the initial value of the volume and V2 is the

final value.
Constant-Pressure Processes
In some chemical reactions and some phase
changes the system is open to the atmosphere
and Pext is equal to the barometric pressure,
which is nearly constant. In this case we can
assume that P(transmitted) is equal to Pext and
to P. We can write
Expansion Processes
If P is larger than Pext the system will expand against
the surroundings. If the process is not too rapid, we
can assume to a good approximation that
P(transmitted) is equal to Pext, although we cannot
assume that is equal to P. The details of the
nonuniformity of the system’s pressure are not
important, because P does not enter into the formula
for w. We can write
 Because P must be greater than Pext for the irreversible process to occur, wsurr will
be smaller for the irreversible expansion than for an equivalent reversible expansion.
Compression Processes
If P is smaller than Pext, a fluid system will be
compressed to a smaller volume. If the process is
irreversible, the system’s pressure will be
nonuniform. It will be compressed to a greater extent
near the piston than in the rest of the system, so that
P(transmitted) will be greater than the equilibrium
pressure of the gas, but smaller than Pext. We are
not prepared to discuss a nonuniform pressure and
will not attempt calculations of w for an irreversible
[Link] can obtain some limits for the work
done.
Bài tập số 1
2.2. Heat
Joseph Black was the first to distinguish between the
quantity of heat and the “intensity” of heat
(temperature) and to recognize latent heat absorbed
or given off in phase transitions.
Heat Transferred during Temperature Changes
A small amount of heat added to a system is
proportional to its change in temperature of the
system if there is no phase change or chemical
reaction:

where dq is an infinitesimal amount of heat

transferred to the object and dT is a resulting
infinitesimal change in temperature. The
proportionality constant C is called the heat
capacity of the system.
* If the temperature is changed at constant pressure,
the heat capacity is denoted by CP and is called the
heat capacity at constant pressure.
* If the temperature is changed at constant volume,
the heat capacity is denoted by CV and is called the
heat capacity at constant volume.
These two heat capacities are not generally equal to
each other.
The specific heat (better called the specific heat
capacity) is denoted by c and is defined as the heat
capacity per unit mass,
where m is the mass of the object. For a pure
substance the molar heat capacity is denoted by Cm
and is defined as the heat capacity divided by the
amount of the substance measured in moles. We will
use both the molar heat capacity at constant
Pressure

and the molar heat capacity at constant volume

Both of these molar heat capacities are intensive
variables. It is an experimental fact that the heat
capacity of any object is always positive.
If an object is heated from temperature T1 to
temperature T2 without any chemical reaction or
phase change occurring, the quantity of heat
transferred to the object is given by
If the heat capacity is independent of temperature

A positive value of q indicates heat transferred to the

system and a negative value indicates heat transferred
from the system to its surroundings.
The calorie was the first metric unit of heat and was
originally defined as the amount of heat required to
raise the temperature of 1 gram of liquid water by 1 ◦C
at 15◦C. The specific heat capacity of liquid water
equals 1.00 calK−1 g−1 at 15◦C. The calorie is now
defined to equal 4.184 J (exactly)
Bài tập số 2
The heat capacities of gases are often more strongly
temperature dependent than those of liquids. If the heat
capacity depends on temperature, it can be represented by
a polynomial or other function.
Heat Transferred during Phase Changes
When a phase change occurs, heat can be
transferred to or from the system without changing its
temperature or its pressure. This heat is sometimes
called latent heat.
The amount of latent heat per unit mass is
characteristic of the substance and the phase
transition.
•The latent heat of fusion (melting) is denoted by
ΔfusH. For water at 0◦C and a constant pressure of
1.000 atm ΔfusH equals 79.72 cal g−1.
•The latent heat of vaporization (boiling) is denoted
by ΔvapH. For water at 100◦C and 1.000 atm ΔvapH
equals 539.55 cal g−1.
2.3. Internal Energy:The First Law of
Thermodynamics
Based on the experiments of Rumford, Mayer,
Helmholtz, Joule, and many others since the time of
Joule, we now state the first law of thermodynamics
as it applies to a system whose kinetic and potential
energy do not change: For a closed system and for
any process that begins and ends with equilibrium
states

where q is the amount of heat transferred to the

system and w is the work done on the system and
where ΔU is the change in the value of U, the internal
energy, which is a state function:
Since the internal energy is a state function we can
write

The internal energy is a state function, but heat and

work are not state functions.
the internal energy U is a macroscopic state function,
it must include the energies of the atoms or
molecules making up the system: translational energy
and electronic energy, and molecules also have
rotational and vibrational energy
2.4. Calculation of Amounts of Heat and Energy
Changes
Like work, heat is not a state function. The amount of
heat put into a system can depend on the path taken
from the initial to the final state, as was the case with
work.
The Heat Capacity at Constant Volume
For a closed simple system at equilibrium n is fixed
and we can choose T and V as independent
variables:
where CV is the heat capacity at constant volume. Although the heat capacity in general
is not a derivative of any function, the heat capacity at constant volume of a simple
closed system is equal to the partial derivative of U with respect to T .
The Ideal Gas as an Example System
It is found experimentally that all gases at
sufficiently low pressure (dilute gases) obey
the ideal gas equation of state to an adequate
approximation:

Dilute gases also have an internal energy that

is independent of the volume or the
pressure:
To an excellent approximation, the heat capacities at
constant volume of monatomic gases are given by

If the vibrational and electronic motions of molecules

can be ignored, then:
Amounts of Heat Transferred to an Ideal Gas
In an isothermal reversible expansion or compression
of a closed ideal gas, ΔU vanishes so that

where V2 is the final volume and V1 is the initial

volume. We will apply this equation to dilute
gases, but must remember not to apply it to
other systems.
Since U depends only on T and n for an ideal gas,

For an ideal gas with fixed n (a closed system)

The Joule Experiment
The first attempt to determine whether (∂U/∂V)T ,n vanishes for
real gases was made by Joule around 1843. His apparatus is
schematically depicted in Figure 2.5.
Because the surroundings were not affected during the
expansion into a vacuum, w was equal to zero. The gas
expanded rapidly so there was little opportunity for heat to be
transferred to or from the surroundings, and q therefore
vanished to a good approximation. From the first law, ΔU was
equal to zero. If a change in temperature of the gas occurred,
heat would be transferred to or from the surroundings after the
expansion was complete, and the final temperature of the
surroundings would differ from the initial temperature. If the
heat capacity of the apparatus and the heat capacity of the gas
are known, the change in temperature of the gas could be
calculated.
The Joule experiment was carried out several times
with various volumes for the second chamber. The
ratio ΔT/ΔV would be determined for each experiment
and extrapolated to zero value of ΔV, where ΔV is the
final volume of the gas minus its initial volume. This
extrapolation is equivalent to taking the mathematical
limit, so the result is a partial derivative, called the
Joule coefficient and denoted by μJ:

The Joule coefficient is related to (∂U/∂V)T ,n by use of

the cycle rule. Values of (∂U/∂V)T ,n for real gases:
Joule was unsuccessful in his attempt to measure the
Joule coefficient because the changes in temperature
that occurred were too small to be measured by his
thermometers, even though he used pressures up to
22 atm. Later versions of the experiment with better
apparatus have given nonzero values of (∂U/∂V)T ,n for
real gases.
There are better ways than the Joule experiment to
determine values of (∂U/∂V)T ,n, and we will discuss
them in Chapter 4. Once values for CV and for
(∂U/∂V)T ,n are obtained, ΔU can be calculated for any
process that begins with one equilibrium state and
ends with another equilibrium state.
Bài tập số 3
Reversible Adiabatic Processes
An adiabatic process is one in which no heat is
transferred to or from a closed system, so that dq is
equal to zero for every infinitesimal step of the
process:
We first assume that CV is constant. We can solve
Eq. (2.4-19) by separation of variables:




If the initial values V1 and T1 are specified, this

equation gives T2 as a function of V2. If we drop the
subscripts on V2 and T2, we can write Eq. (2.4-21a) in
the form:
Equation (2.4-21) can be used for a
reversible adiabatic compression as well
as for an expansion. It is an example of an
important fact that holds for any system,
not just an ideal gas:
For a reversible adiabatic process in a
simple system the final temperature is a
function of the final volume for a given
initial state.
Irreversible Adiabatic Processes
We have assumed that we can equate
P(transmitted) and Pext for a relatively slow
irreversible expansion processes. As an
example, consider the expansion of
Example 2.21 if it occurs irreversibly with a
constant external pressure.
1
2.5. Enthalpy
Many liquid systems in the laboratory are
contained in vessels that are open to the
atmosphere and are thus maintained at a
nearly constant pressure. For convenient
analysis of constant-pressure processes we
define a new variable, denoted by H and
called the enthalpy:
The enthalpy is a state function because U, P,
and V are state functions. We will refer to
these conditions simply as constant-pressure
conditions and assume that P(transferred) = P =
Pext. For a process under such conditions,
The heat transferred to the system is given by

From Eq. (2.5-1)

At constant pressure the VdP term vanishes,

so that

For a finite process,

The Heat Capacity at Constant Pressure
The heat capacity at constant pressure is given by

The heat capacity at constant pressure is the most

commonly measured heat capacity for solids and
liquids. We now obtain an expression for the
difference between CP and [Link] begin with

There is no V(∂P/∂T ) term because P is held

constant in the differentiation.
the relation
We substitute this equation into Eq. (2.5-9) and use the
fact that CV = (∂U/∂T )V,n to write

For an ideal gas, (∂U/∂V)T ,n = 0 and

(∂V/∂T )P,n = nR/P, so that

The physical explanation for this difference between CP

and CV is that heating an ideal gas at constant volume
does not work on the surroundings. In heating at
constant pressure some of the heat is turned into work
against the external pressure as the gas expands.
Equations (2.3-10) through (2.3-12) together with Eq.
(2.5-12) give the following relations for dilute gases:

Equation (2.5-13a) is a good approximation. The other

two equations are fairly good approximations near
room [Link] the approximations in Eq. (2.5.13)
are not adequate, CP,m can be represented by
the polynomial
The ratio of the constant-pressure heat capacity to the
constant-volume heat capacity is denoted by γ:
The Joule–Thomson Experiment
For an ideal gas U depends only on T and n, so that H
depends only on T and n:

Therefore,

Joule and Thomson carried out experiments in the

1850s to determine the value of (∂H/∂P)T ,n for real
gases.
=

Joule–Thomson coefficient
2.6. Calculation of Enthalpy Changes of
Processes without Chemical Reactions
The most useful calculations of ΔH are for constant-
pressure processes in closed systems. If no phase
change or chemical reaction occurs,

The integration in this formula is carried out on

a constant-pressure path.
To calculate ΔH for the fusion of n moles of a
substance we write

where ΔfusHm is the molar enthalpy change of fusion.

For the vaporization of n moles of a substance

where ΔvapHm is the molar enthalpy change of

vaporization of the substance.
Since the enthalpy is a state function, we can
calculate ΔH for a given process by calculating ΔH
for any process having the same initial and final
states.
Bài tập số 4
Although ΔH is the same for any process
with the same initial and final states as
the overall process in Example 2.26, q and
w are dependent on the path of a particular
process. If the pressure is not constant
during the entire process, q is not
necessarily equal to ΔH.
Enthalpy Changes for Irreversible
Processes
Consider an irreversible process that begins
with an equilibrium and ends with an
equilibrium state. To calculate ΔH for such an
irreversible process, we find a reversible
process with the same initial and final states,
calculate ΔH for that process, and assign that
value to the irreversible process, using the fact
that H is a state function.
Bài tập số 5

Hfus=120,2 kJ
2.7. Calculation of Enthalpy Changes of a Class of
Chemical Reactions
A chemical reaction involves the breaking of some chemical
bonds and/or the formation of other chemical bonds. The
breaking of bonds requires an input of energy and the
formation of bonds gives off energy, so that nearly every
constant-temperature chemical reaction is accompanied by
energy and enthalpy changes.
- If the system gives off heat when a reaction takes place at
constant temperature, the reaction is called exothermic.
- If the system absorbs heat at constant temperature, the
reaction is called endothermic.
In this chapter we will consider only chemical reactions in
which every reactant or product is either a gas or a pure liquid
or solid, and we will assume that all gases are
ideal gases. Three reactions in this class are:
Physical chemists like to write a single equation that can apply
to every possible case. In order to do this, we write chemical
reaction equations with the symbols for all substances on the
right-hand side and replace the → symbol by an equals sign.
The three reactions of Eqs. (2.7-1) through (2.7-3) become
We denote the stoichiometric coefficient of substance
number i by νi or by ν(Fi), where Fi represents the
chemical formula of the substance. If substance
number i is a product, νi is positive, and if substance
number j is a reactant, νj is negative.
If NO2 is called substance number 1 and N2O4 is
called substance number 2, then ν1 = ν(NO2) = 2 and ν2
= ν(N2O4) = −1 in Eq. (2.7-6). If the number of
substances involved in the reaction is represented by
s, we number the substances from 1 to s, and
represent any chemical reaction by the equation
If all substances are either pure liquids or
solids or ideal gases the enthalpy of the
system is a sum of contributions of the
separate substances

where Hm(i) is the molar enthalpy (enthalpy per

mole) of substance number i and ni
is the amount (in moles) of that substance.
Consider a chemical reaction that begins with
reactants in equilibrium at some particular
temperature and pressure and ends with products in
equilibrium states at the same temperature and
pressure. The enthalpy change of the reaction is
given by

where Δni is the change in the amount of substance

number i. We say that one mole of reaction occurs if

for each substance. That is, a number of moles of a

product appears that is equal to that product’s
stoichiometric coefficient, and a number of moles of a
reactant disappear that are equal to the magnitude of
its stoichiometric coefficient.
For 1 mol of reaction,

The molar enthalpy of any substance depends on its state.

The standard state of a liquid or solid substance is specified to
be the pure substance at a fixed pressure of exactly 1 bar
(100,000 Pa), which we denote by P◦. The standard state for a
gas is defined to be the corresponding ideal gas at pressure
P◦. The difference between the molar enthalpy of a real gas at
1 bar pressure and the corresponding ideal gas at 1 bar is
numerically very small.
If substance number i is in its standard state, its molar
enthalpy is denoted by H◦m (i).
A standard-state reaction is one in which all substances are in
their standard states before and after the reaction. The
enthalpy change for a standard-state reaction is denoted by
ΔH◦. The standard-state pressure was at one time defined to
equal 1 atm (101,325 Pa).
We use the standard-state enthalpy change of
formation to calculate ΔH◦ for chemical reactions. The
standard-state enthalpy change of formation of
substance i is denoted by ΔfH◦(i).
The enthalpy change for 1 mol of any standard-state
reaction in our restricted class is given by

We now invoke Hess’s law, which states: The

enthalpy change of any process that is equivalent to
successively carrying out two other processes is
equal to the sum of the enthalpy changes of those
two processes.
This equation applies only if the final temperature is equal to
the initial temperature.

If the formation reaction for a substance cannot actually be

carried out, the enthalpy change of formation can be
calculated from the enthalpy change of other reactions that
can be combined to give the reaction of interest, using Hess’s
law.
Enthalpy Changes at Various Temperatures
An enthalpy change for a reaction at a temperature
other than a temperature found in a table can be
calculated from heat capacity data. Consider the
processes shown in Figure 2.10. The reaction at
temperature T2 is the process whose enthalpy
change we want to find. Call it process 2. An
alternate pathway with the same initial and final
states consists of processes 3, 1, and 4. Process 3 is
the change in temperature of the reactants from T2 to
T1. Process 1 is the chemical reaction at temperature
T1, with a known enthalpy change. Process 4 is the
change in temperature of the products from T1 to T2.
According to Hess’s law ΔH(T2) is equal to the sum of
the enthalpy changes of processes 1, 2, and 3:

For 1 mol of reaction, process 3 consists of changing

the temperature of an amount of each reactant equal
to the magnitude of its stoichiometric coefficient, so
that

Where CP,m(i) is the molar heat capacity of substance

i. The second equality comes from interchanging the
limits of integration and realizing that the
stoichiometric coefficients of reactants are negative.
Process 4 is the change in temperature of the
products from T1 to T2, so that

The sums in Eqs. (2.7-17) and (2.7-18) can be

combined to give the expression

where
ΔCP is the heat capacity of the appropriate
numbers of moles of products minus the heat
capacity of the appropriate numbers of moles
of reactants. If ΔCP can be assumed to be
constant, Eq. (2.7-19) becomes

Remember that this equation applies only if

the reactants and the products are both at
temperature T2.
Adiabatic Chemical Reactions
We have discussed reactions in which the final
temperature is the same as the initial temperature.
The enthalpy change will have a different value if the
temperature of the system changes during the
reaction. One case of interest is that the chemical
reaction takes place adiabatically at constant
pressure. In this case the enthalpy change is equal
to the heat transferred, which is equal to zero. In
order to compute the final temperature of a system in
which a chemical reaction takes place adiabatically,
we consider the processes shown in Figure 2.11.
Process 1 is the adiabatic reaction, for which ΔH is
equal to zero. Process 2 is the reaction carried out
isothermally. Process 3 is the change in temperature
of the products plus any remaining reactants to the
same final state as process 1. Because enthalpy is a
state function, the enthalpy change of process 1 is
equal to the sum of the enthalpy changes of
processes 2 and 3:

If a stoichiometric mixture is taken and if the reaction

proceeds to completion, there are no remaining
reactants, and we can write
2.8. Calculation of Energy Changes of Chemical
Reactions
It would be possible to make tables of energy
changes of formation and to calculate
ΔU values in the same way as ΔH values are
calculated from enthalpy changes of formation.
However, adequate accuracy can be achieved
without constructing a table of Δ fU values. From the
definition of the enthalpy we can write an expression
for ΔU for a chemical reaction:

Ordinarily Δ(PV) is much smaller than ΔH

The product PV is given by

Under ordinary conditions the molar volume of a gas

is several hundred to a thousand times larger than
the molar volume of a solid or liquid. If there is at
least one gaseous product or reactant we can ignore
the volume of the solid and liquid phases to an
adequate approximation,
If the products and reactants are at the same
temperature and if we use the ideal gas equation as
an approximation,

where Δn(g) is the change in the number of moles of

gaseous substances in the reaction equation. If 1 mol
of reaction occurs, then

which defines the quantity Δν(g), equal to the number

of moles of gas in the product side of the balanced
chemical equation minus the numbers of moles of
gas in the reactant side of the balanced equation.
Average Bond Energies
To estimate the energy change for a gas-phase
reaction, you can write
The error of 9 kJ mol−1 in the previous example is
typical. It is larger than the difference between ΔH
and ΔU, so that the value of ΔU obtained from
average bond energy values is ordinarily used for ΔH
without correction for the value of Δ(PV). Average
bond energies are used only if accurate enthalpy
changes of formation are not available, since the
results are only approximately correct. Average
bond energies cannot be used for reactions involving
solids or liquids, where intermolecular forces make
important contributions.