Physical

Chemistry:
Thermodynamics,
Structure, and
Change
Tenth Edition

Chapter 2

The First Law

Fall 2017
CHAPTER 2: FIGURE 2A.1
CHAPTER 2: FIGURE 2A.2
 CHAPTER 2: 2A Internal energy

Diathermic (Diabatic) System: A system in which energy is allowed in

and out in the form of heat - system in thermal contact with surroundings
Adiabatic System: A system in which heat is not allowed in or out

(a) Endothermic Process:

Process that absorbs heat
(b) Exothermic Process:
Process that releases heat
(c) Endothermic process
in a diathermic container:
decreases temperature of
surroundings
(d) Exothermic process in
a diathermic container:
increases temperature of
surroundings
CHAPTER 2: FIGURE 2A.3
CHAPTER 2: FIGURE 2A.4
 CHAPTER 2: 2A Internal energy

Internal Energy
Internal Energy (U): total energy of a system at any given time
it comes from the total kinetic and potential energy of
molecules which compose the system

Change in Energy (U): Change in U as system goes from an

initial state with energy Ui to final state with Uf
U = Uf - Ui
Internal energy is:
a state function: only depends on the current state, not on preparation of
the state.
an extensive property: is dependent upon the amount of matter Properties
whose values are increased/decreased in direct proportion to the
enlargement/reduction of the system

Recall that an intensive property is independent of the amount of matter - all of the
thermodynamic driving forces are selected from among properties of this type.
 CHAPTER 2: 2A Internal energy

First Law
The internal energy of an isolated system is constant.

Internal energy of a system can be changed by:

1. Doing work to the system (w)
2. Energy transferred as heat to the system (q)

U=q+w
Heat and work are equivalent ways of changing the energy of a system.
System is like a bank, where currencies can be deposited or withdrawn.
If a system is completely isolated from its surroundings: no change in the
internal energy takes place: U = 0 (no perpetual motion)
 CHAPTER 2: 2A Internal energy

Expansion Work
1. Work required to move an object over distance dz
against a force of opposing magnitude F:
dw = -Fdz
Negative sign: since the system moves against the
opposing force F, there will be a decrease in the
internal energy of the system

2. System: massless, frictionless, rigid, perfectly

fitting piston of area A

3. Force on outer face of the piston: F = pexA

4. Work done against external pressure:

dw = -pexAdz

5. Change in volume dV = Adz

 CHAPTER 2: 2A Internal energy

Expansion Work
Work can now be written in terms of pressure and change in volume:

dw = - pex dV
If we need to know the total work done expanding the volume of a system, we can
integrate the above expression over the initial and final Volumes

Force acting on the piston, pex A, is the same as raising a weight as the system
expands (e.g., F = mg)
Compressing the system is analogous, excepting that Vi > Vf

If we have free expansion, there is no opposing force, despite increase (or decrease
for compression) in volume. (e.g., expand into vacuum)
w=0
CHAPTER 2: FIGURE 2A.5
CHAPTER 2: FIGURE 2A.6
 CHAPTER 2: 2A Internal energy

Isothermal Reversible Expansion

Expansion is isothermal if system is in contact with constant
thermal surroundings (i.e., a constant temperature bath or heating
element)

1. Each stage of expansion, p = nRT/V

2. Temperature T is constant, so treated outside of the integral

When Vf > Vi, gas expands, and work done to expand the gas
causes the system to lose internal energy, w < 0
CHAPTER 2: FIGURE 2A.7
 CHAPTER 2: 2A Internal energy

Heat Transactions
Internal energy can be written as:
dU = dq + dwexp + dwe
dq heat: energy transferred across boundary due to difference in T
dwexp work due to expansion
dwe extra sources of work (e.g., electrical current)

At constant V, dwexp = 0 (system cannot expand)

If no additional work (no battery, etc.), dwe = 0

dU = dq
Write dU = dqv, which implies infinitessimal change at constant volume.
Thus for a measurable finite change:
U = qV
q > 0 (heat supplied to system), q < 0 (heat lost from system)
CHAPTER 2: FIGURE 2A.8

PCHEM 2 LAB
 CHAPTER 2: 2A Internal energy

How does the calorimeter work?

1. Reaction is conducted in the constant volume bomb
2. Bomb is immersed in a stirred water bath, forming the
calorimeter
3. Calorimeter is immersed in a second water bath, the
temperature of which is continuously adjusted to the temperature
of the bomb bath, thereby ensuring an adiabatic system

A chemical reaction either releases or absorbs heat, causing a

proportional change in temperature T of the calorimeter:

Measuring T allows us to determine qV, and therefore U -

BUT....
we must calibrate the calorimeter using known energy to get the
calorimeter constant, C
q = CT
 CHAPTER 2: 2A Internal energy

Heat Capacity & Internal Energy

Here is a plot of the internal energy of a system versus temperature

The slope of the curve at a given temperature is

defined as the heat capacity of the system
The heat capacity at constant volume is formally
defined as

The RHS is a partial derivative, which is a

derivative where all variables are held constant
except for one - it gives the slope of the plot of U
vs. T

The heat capacity at temperature A is lower than

that at temperature B
 CHAPTER 2: 2A Internal energy

Relating U and T at Constant V

Heat capacity is used (say in a calorimeter) to relate internal energy changes and
changes in temperature
dU = CV dT at constant volume

As usual, an infintessimal change in temperature changes energy slightly Over a

measurable range of temperatures
U = CV T at constant volume

Change in energy can be noticed with heat supplied at a constant V

qV = CV T

1. Supply a controlled known amount of heat to the sample (say with an electric current
in a heater)
2. Monitor the resulting increase in temperature
3. The ratio: heat supplied/temperature increase is the heat capacity

Large heat capacity: large supply of heat, small change in measured T

Small heat capacity: small supply of heat, large change in measured T
Infinite heat capacity: at a phase transition, energy changes phases!
CHAPTER 2: FIGURE 2A.9
CHAPTER 2: FIGURE 2A.10
 CHAPTER 2: 2B Enthalpy

Enthalpy For a system that changes volume, the internal energy is

not equal to the heat supplied, as for a fixed volume
system

Some energy supplied as heat to the system returns to

surroundings as expansion work:
dU < dq, because dU = dq + dw

When heat is supplied to the system at a

constant pressure (e.g., reaction containers open to
atmosphere), another thermodynamic state function
known as enthalpy, H, can be measured accurately:

H = U + pV
Change in enthalpy is equal to heat supplied to the
system at constant pressure
dH = dq H = qp
CHAPTER 2: FIGURE 2B.1
 CHAPTER 2: 2B Enthalpy

Variation of Enthalpy with Temperature

Enthalpy of substance increases as T is raised - How H changes is
dependent on the conditions, most important being constant pressure

The heat capacity at constant pressure is an

extensive property, defined as

For infinitessimal changes in temperature

dH = CpdT (at constant pressure)

and for measureable changes

H = Cp T (at constant pressure)

and heat at constant pressure

qp = Cp T
Also: intensive property of molar heat
capacity at constant pressure, Cp,m
CHAPTER 2: FIGURE 2B.3
 CHAPTER 2: 2C Thermochemistry

Thermochemistry
Thermochemistry is the branch of thermodynamics which studies heats of
reaction: heat produced by or required for a chemical reaction.
In thermochemistry, chemical reactions are divided into two categories:

exothermic reaction
qrxn < 0; heat is produced by the reacting system (i.e., the temperature of
the system is higher right after the reaction than initially; heat must be
transferred from the system to the surroundings in order to return the system to
its initial temperature)

endothermic reaction
qrxn > 0; heat is absorbed by the reacting system (i.e., the temperature of
the system is lower right after the reaction than initially; heat must be
transferred from the surroundings to the system in order to return the system to
its initial temperature)

These reactions can also be described in terms of enthalpy, H

 CHAPTER 2: 2C Thermochemistry

Standard Enthalpy Changes

Numerical values describing U or H of a system when some chemical or physical
change occurs depend upon the nature of the reaction, as well as the physical states of
reactants and products

It is useful to define a standard enthalpy change, Ho, which is the change in enthalpy
for a process (chemical or physical) where initial and final substances are in standard
states

standard states: pure form of a substance at specified temperature at pressure of 1

bar, e.g. standard state of liquid water at 298 K is pure liquid water at 298 K and 1 bar

Examples:The standard enthalpy of vapourization, vap Ho, is change in enthalpy per

mole when pure liquid vapourizes to pure gas at pressure of 1 bar. The standard
enthalpy of fusion, fus Ho, is enthalpy change accompanying change from liquid to
solid
H2O(l) H2O(g) vap Ho(373 K) = +40.66 kJ mol-1
H2O(s) H2O(l) vap Ho(273 K) = +6.01 kJ mol-1

Ho can be reported at any temperature, convention is at 298.15 K

 CHAPTER 2: 2C Thermochemistry

Enthalpy of Physical Change

 CHAPTER 2: 2C Thermochemistry

Graphical Depiction of Enthalpies of Transition

CHAPTER 2: 2C Thermochemistry

Hess Law
CHAPTER 2: TABLE 2C.2
 CHAPTER 2: 2C Thermochemistry

Enthalpies of Chemical Change

 CHAPTER 2: 2C Thermochemistry

Standard Molar Enthalpies

 CHAPTER 2: 2C Thermochemistry

Reaction Enthalpy in Terms of Formation

CHAPTER 2: 2D State functions and exact differentials

State vs. Path Functions

CHAPTER 2: 2D State functions and exact differentials

State Functions
CHAPTER 2: FIGURE 2D.1
CHAPTER 2: FIGURE 2D.2
CHAPTER 2: FIGURE 2D.3
CHAPTER 2: FIGURE 2D.5
 CHAPTER 2: 2D State functions and exact differentials

Changes in Enthalpy at Constant Volume

 CHAPTER 2: 2D State functions and exact differentials

Three important coefficients

1. Thermal expansion coefficients

Heat
T1 T2
V = T V
 CHAPTER 2: 2D State functions and exact differentials

Three important coefficients

2. Isothermal compressibility

Press
P1 P2
V = - kT p V
CHAPTER 2: TABLE 2D.1
 CHAPTER 2: 2D State functions and exact differentials

Three important coefficients

3. Joule-Thomson effect

P1 > P2
P1 P2
T1 T2
T = p
CHAPTER 2: FIGURE 2D.6
CHAPTER 2: FIGURE 2D.7
 CHAPTER 2: 2E Adiabatic changes

Adiabatic Changes
What changes occur when a gas expands adiabatically?
Work is done - internal energy falls
Temperature of the working gas falls
Kinetic energy of the molecules falls with average speed of the molecules
CHAPTER 2: 2E Adiabatic changes
CHAPTER 2: 2E Adiabatic changes

Adiabatic Changes
CHAPTER 2: 2E Adiabatic changes
Cp - Cv = R