The First Law of

Thermodynamics

1
 Thermodynamics
Statistic
Macroscopic Microscopic

Universe Surr.

Systems
Sys. Walls

2
 Processes

Isobaric P = Const.
Isothermic T = Const.
Isometric V = Const. Reversible
dx ( )

V, E, Cp Functions
Exothermic Endothermic

a) Extensive

T, r
State x = y = z x

b) Intensive Trajectory x y z y

3
 Exothermic and Endothermic
Reactions
A reaction that releases heat is exothermic.
A reaction that absorbs heat is endothermic.

The reaction we considered on the preceeding slide is

exothermic. Endothermic reactions are much less frequent.
We will see later that entropy must account for the fact
that such reactions can be spontaneous.

An example of an endothermic reaction is the dissolution of

sodium nitrate in water. This reaction is the basis of instant
cold packs that are included in first aid kits.

4
 Equilibrium and Steady-state
State that can exist in an isolated system
Equilibirum: Remains constant indefinitely
There is not mass or energy exchange with the Surr.
Each phase, fluid or part of
the system have the same Dynamic
M1 M2
uniform X thermodynamical Static
property
TM TM
M1 = M2

State that can exist in an open system

Steady-state: Constant over time
There is mass or energy exchange with the Surr.

Is not a fact that each phase, T

0
fluid or part of the system t
have the same uniform X q
TH TC
thermodynamical property 5
 The Conservation of Energy
Energy in thermodynamics is the capacity to do work.
The work occurs against an opposing force and can
be defined as a force operating through a distance.
When chemical change used to generate work there is
often heat generated as well. We will show in this lecture
that the sum of the heat generated and the work done is
a constant amount of energy. Thus, the first law of
thermodynamics is an expression of the conservation of
energy.

Internal Energy = Heat Exchanged + Work Done

6
 Internal Energy
Now that we have given a symbolic form to both heat (q) and
work (w) we can state the first law in terms of symbols.

DU = w + q

The symbol U represents the internal energy of the system.

This is the energy that is conserved. The first law states that
any change in the internal energy, DU, results either from
work done or heat exchanged with the surroundings.
We can also state the first law in differential form.

dU = dw + dq

In this case there is an important difference between the

differential written with d and that written with d. 7
 Energy
The total energy is conserved It is impossible to construct a device that
operates in a cyclical manner and performs
DU = Uf Ui = w + q work without the input of energy (Heat)
(Internal energy) to the device

DUT =DUSys + DUSurr

PExt = Pin PExt > Pin Extensive!

Work
(w)

Organized!
1 q 2 Heat
Random! (q)
8
T1 < T2
 State Functions
and Path Functions
We shall show that the internal energy is state function.
A state function is not dependent on the path used to get
to a certain set of parameters. For a given value of the
variables T and V the value of internal energy, DU, is fixed
and does not depend on the path.

On the other hand the work and the heat are not state
functions. The magnitude of each of them depends on
the particular path in a given process. We express this
as follows:
U2

dU = U2 U1 = DU , dw = w , dq = q
U1

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 Work and Heat
We consider a chemical reaction that generates both work
and heat. For example,

Zn(s) + 2 HCl(aq) ZnCl2(aq) + H2(g)

Note that one mole of H2 gas is produced for each equivalent

of Zn consumed. If the reaction takes place in a container
that is fitted with a piston the production of gas will cause the
piston to rise.
work

Reaction heat
10
taking place
 Work and Heat
If we constrain the piston so that it cannot move, then the
pressure in the container will rise. This will result in an
increase in the temperature (PV = nRT). Thus, more heat
will be released into the surroundings in this case.

Although we have not accounted for the difference

quantitatively, we know that energy must be conserved
and so the amount of heat released must equal the work
that would have been done.
work

Reaction heat
11
taking place
 Pressure-Volume Work
Students often wonder why we begin with pressure-volume work.
After all, there are lots of kinds of work starting with the basic
definition that work is a force acting through a distance.
However, the work performed by an engine involves the
expansion of a gas to drive a piston and it is this work that
is of practical interest in the design of steam and internal
combustion engines. It is also pressure-volume work that
leads most directly to an understanding of the relationship
between heat and work. In order to study the transfer of energy
in the form of heat and work we define the system (the engine
or mechanical device we are interested in) and the surroundings.
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 The measurement of work
Work is defined as the result of a force acting through a
distance. This easily seen for gravitation. If an object of
mass m is lifted to a higher elevation in the gravitational field
of the earth the work done is w = mgh.
h2 h2

dw = Fdh = mg dh = mg(h 2 h 1)
h1 h1

The units of work are kg m2/s2 , which are also called Joules.
Equivalent sets of units are listed below:
1 J = 1 Nm = 1 Pa m3 = 1 kg m2s2
Just as there is a sign associated with work of lifting (or letting
something fall) in a gravitational field, there is a sign
associated with work done and heat exchanged by the system.
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 The Sign Convention
We can summarize the sign convention in the following table.

Energy + (increased) - (decreased)

Work done (w) on system by system
Heat flows (q) into system from system

Alternatively, we can depict the convention as follows.

w<0 w>0 q<0 q>0 14

 The Sign Convention
We can summarize the sign convention as follows:
1. Choose the correct answer
A. Work done by the system is positive
B. Work done by the system is negative

2. Choose the correct answer

A. Heat absorbed by the surroundings is positive
B. Heat absorbed by the surroundings is negative

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 latihan
1. Calculate the work needed for a 65 kg person to climb through 4.0 m
on the surface of the Earth.
2. Calculate the work performed by a person who exerts a force of 30N
to move a box 30m if the force were (a) exactly parallel to the
direction of movement, and (b) 45o to the direction of movement.

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17
 Irreversible expansion

Fig 2.7 Work done by a gas

when it expands against a
constant external pressure

w Pex dV
i
f

Pex dV Pex ( Vf Vi )
i

w Pex V
The figure illustrates condition that
occasionally occurs with gases; the
expansion of a gas into a large volume
which is initially a vacuum. In such a
case, since the gas is expanding against
a pext of 0, by the definition of work , the
work done by the gas equals zero. Such
a process is called a free expansion

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 Reversible expansion
Fig 2.8 Work done by a gas
when it expands isothermally
against a non-constant external
pressure.

Set Pex = P at each step of

expansion

System always at equilibrium

f

w Pex dV
i

Since Pex is not constant, it

cant be brought out
 Isothermal reversible expansion
f

w Pex dV
i

Since Pex is not constant, it cant be brought out

However, Pex depends on V, so substitute using PV = nRT

f
dV
w nRT
V
i
Vf
nRT ln
Vi
 Isothermal Processes
For an ideal gas the internal energy is the kinetic energy. There is
no potential energy for an ideal gas so this must be true.
Therefore, For an isothermal process T2 = T1 = constant so

U = 3 nRT , Um = 3 RT
2 2
The internal energy change is always zero for an isothermal
process. If we return to the first law we see that
DU = U2 U1= 3 nRT2 3 nRT1 = 0
2 2

The system absorbs heat from the surroundings with an energy

equal to the work done.
DU = w + q = 0
q=w
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 Isochoric and Isobaric Processes
Isochoric means constant volume. The red line in the preceeding
figures is a constant volume process. In such a process w = 0
since dV = 0 (Recall that dw = -PdV).
Therefore, DU = qV for an isochoric process. The V subscript
means that V is held constant. Isobaric means constant pressure.
In a constant pressure expansion such as we saw in the preceeding
frames we know how to calculate the work, w = -PextDV.
Moreover, we know that DU for the isochoric process is -qV. Since
the end point of the isochor and isobar is the same as that for the
isotherm, we know that overall DU = 0.
Therefore, qP = qV + PextDV.
The system absorbs heat from the surroundings with an energy
equal to the work done.

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 Question
Which expression correctly gives the work of expansion
(V2 > V1)?

V2
A. nRT ln
V1
V2
B. nRT ln
V1
V2
C. nR ln
V1
V2
D. nR ln
V1
1. Gas in a piston chamber kept in a constant-temperature
bath at 25oC expands from 25ml to 75ml very slowly as
illustrated in figure. If there is 0,001 mole of ideal gas in
the chamber, calculate the work done by the system
2. A sample gas changes in volume from 4L to 6L against
an external pressure of 1,5 atm and simultaneously
absorbs 1000J of heat. What is the change in internal
energy of the system?
3. If P1 175 torr, V1 2.00 L, P2 122 torr, V2 5.00 L,find
wrev for process (a) and (b)

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 Heat
wExp=0
dU = wExp + wi + q V = (Const.) dU = dq DU = qV
wi=0

qV=CcalDT

Heat capacity

U
CV
T V
Uf Tf

dU C
Ui Ti
V dT

DU CV DT
V=Const
qV=CVDT Ci=nCi Extensive!
 The measurement of heat
We must carefully distinguish between heat and temperature.
When we add heat to the system its temperature increases.
We can use measurement of the temperature to determine
how much heat has been added. However, we need to know
the heat capacity of the system in order to do this.
Heat supplied
Heat capacity =
Temperature rise
The heat capacity is called C. If we perform a heat exchange
at constant volume then we designate the heat capacity as CV.
If the process occurs at constant pressure we call the heat
capacity CP.
qV,P
CV,P =
DT
 Calorimetry
The science of heat measurement is called calorimetry.
A calorimeter consists of a container in a heat bath.
A physical or chemical process occurs in the container and
heat is added or removed from the heat bath. The
temperature increases or decreases as result. By knowing
the heat capacity of the bath we can measure the amount
of heat that has been added or removed from the system.

Energy in the
form of heat
flows into the bath.
 Calorimetry
In the studies of biological systems there are two important
types of calorimetry.
1. Differential scanning calorimetry (DSC)
2. Isothermal titration calorimetry (ITC)

In DSC the temperature is increased at a constant heating

rate and the heat capacity is measured. DSC is used for
determining the parameters associated with phase transitions
e.g. protein unfolding, denaturation, DNA hybridization etc.

In ITC the temperature is held constant while one component

is added to another. The heat of interaction (e.g. binding) is
measured using this method. ITC is widely used to determine
the enthalpy of binding, e.g. for protein-protein and
protein-drug interactions among other types of biological
applications.
 Molar and Specific Heat
Capacities
We use molar heat capacities for pure substances. As the
name implies the units are J/mol-K for the molar heat
capacity. We write the molar heat capacity at constant
volume as CV,m.

For mixtures we cannot use a molar heat capacity and so

we use the specific heat capacity, which is the heat capacity
per gram of material with units of J/g-K.
 Enthalpy
Appears naturally when
P=Const. and V changes H = U + PV Extensive!

dH dU d PV
dH dU PdV VdP dU

dH dq dw PdV VdP
Relation between DH and DU dw
dH dq PdV PdV VdP
DH = DU + DPV)
dH dq VdP
For an isothermal change P=Const.
of an ideal gas (PV=nRT) dH dqP
DH = DU + DnRT)
Where Dn=n(g)P-n(g)R
For liquids and solids
DV0
DH DU
 Calculating the
internal energy change
We have seen that the internal energy depends only on
temperature. For example, for a change of pressure
(and temperature) at constant volume we saw that DU = qV
since the work is zero for a constant volume process.
Thus, at constant volume:
DU = qV = CVDT
But, in fact when we consider the origin of the internal energy
in the kinetic theory of gases we realize that:
DU = 3 nRDT = CVDT
2
and therefore:
CV = 3 nR and CV,m = 3 R
2 2
 The heat capacity
at constant pressure
For a constant pressure step we saw in the last lecture that:
qP = qV + PDV
By analogy with the constant volume process:
qP = CPDT
and therefore:
CPDT = CVDT + PDV
CPDT = CVDT + nRDT
CP = CV + nR
so that CP = 5 nR and CP,m = 5 R
2 2
 Definition of the enthalpy
Based on these considerations we can see that there is a
new state function, the energy at constant pressure.
This state function is known as the enthalpy H. The enthalpy
change is:
DH = qP = CPDT
and we can rewrite the relationship from the previous slide as:
DH = DU + PDV
We have also defined the relationship between the internal
energy and the enthalpy. The PDV term represents the work
of expansion (or compression) done against the atmosphere
during a chemical reaction. We use enthalpy instead of
internal energy under normal conditions because it includes
this work automatically.
 Variations of the enthalpy with T
H
CP
T P
Hf Tf

dH C
Hi Ti
P dT

D H C P DT P=Const
qP=CPDT
Ci=nCi Extensive!

Until this point CP CPT)

c
C P ,m a bT
H T2 T2
c
dH C P ,m dT
H T1
dH a bT 2 dT
T1
T
T2

1 1

H T2 H T1 aT2 T1 T2 T1 c
b 2 2

2 T2 T1
 Correlation between CP and CV
For a perfect gas PV = nRT H = U + PV

H = U + nRT

H U dT
CP = CV + nR nR dH = dU + nRdT
T T

Xe (N=1) CV = CV,Trans + CV,Rot + CV,Vib

CV(Xe ) = 3R/2
CV = CV,Trans + CV,Rot + CV,Vib N2 (N=2) CV = CV,Trans + CV,Rot + CV,Vib
CV(N2 ) = 3R/2 + 2R/2
R/2 R/2 R
CV,Vib << 1 @ T 300 K
 Heat Capacity for
a Diatomic Molecule
For a diatomic molecule there is contribution from rotations
as well as translations. This means that as heat is added to
the system the rotational levels can be populated in addition
to an increase in molecular speed. The kinetic theory of
gases considers only the speed. An approximate rule is that
we obtain a contribution to the heat capacity, CV of 1/2nR for
each degree of freedom. We saw that for a monatomic gas
the heat capacity was CV = 3/2nR. A diatomic gas has two
rotational degrees of freedom and so the heat capacity is
approximately CV = 5/2nR. What does this say about CP?
Well, the relationship between CP and CV holds for all gases
so CP = 7/2nR for a diatomic ideal gas.