Chem 467 Review Sheet for Exam 3 Fall 2016

Equations of State for Real Gases

van der Waals EOS – Attempts to account for
Finite volume of molecules (b)
Attractive interactions between molecules (a)

( )
nRT n 2
RT a
This EOS is written as P= −a or P= − 2
V −nb V V m−b V m
Virial EOS – Based on measured behavior of real gases. First we define a compression factor, Z
Vm P Vm
Z= = V om is the molar volume of ideal gas at a given T and P.
o
Vm RT
We then write an expansion of Z in either pressure or reciprocal volume.
P V m =RT (1+ B ' P +C ' P 2+...)
B C
or P V m =RT (1+ + +...)
V m V 2m

Critical Points – Under particular conditions a gas will condense and exist as a liquid and a vapor.
When this coexistence region reduces to a single point in T, V, P space, we refer to this as the critical
point. Critical points are tabulated for most gases as Tc, Vc, Pc. Below Tc, a gas will eventually
condense. The critical points can be related to the parameters in certain equations of state.

Solids and Liquids

Solids are characterized by short intermolecular distances and (in crystalline solids) long-range order.
Liquids have short intermolecular distance and short-range order, but no long-range order. Structure
can be described by the radial distribution function. This function oscillates, but damps with
distance. The many interactions and lack of order make liquids difficult to model.

Mathematical Tools
Total Differentials – For a function of two variables, f (x,y), we can write the total differential

df =    
∂f
∂x y
dx
∂f
∂y x
dy

If there are more than two variables, we write a similar term for each variable, holding all the other
variables constant in each partial derivative.
Partial Derivatives – Partial derivatives obey certain relations

 
∂f
=
1
Reciprocal Rule:
 
∂x y ∂ x
∂f y

Chain Rule:     
∂f
=
∂f
∂ z y ∂x y
∂x
∂z y

Cyclic Rule:    
∂z
∂y x
∂y
∂x z
∂x
∂z y
=−1

Commonly Used Partial Derivatives

Coefficient of Thermal Expansion α= ( )

1 ∂V
V ∂T P

κ =− (
V ∂P)
1 ∂V
Isothermal Compressibility T
T

Intro to Thermodynamics
System and Surroundings – The system is what we care about. The surroundings are everything else.
If a system can exchange mass and energy with the surroundings, it is called “open”.
If a system can only exchange energy with the surroundings, it is called “closed”.
If a system can exchange neither mass nor energy with the surroundings, it is called “isolated”.
State and Path Functions – State functions only depend on the initial and final states. Path functions
depend on the specific path taken between the initial and final states. The state variables, T, P, V and
thermodynamic variables S, U, H, A, and G are all state functions. Work and heat are path functions.
Temperature – According to kinetic molecular theory, relates to the random kinetic energy available to
the molecules. In continuum thermodynamics, it is a property of the system or surroundings associated
with heat flow.
Thermal Equilibrium – Two objects at the same temperature T are in thermal equilibrium.
Zeroth Law of Thermodynamics – If A is in thermal equilibrium with B, and B is in thermal
equilibrium with C, then C is also in thermal equilibrium with A.
Pressure – According to kinetic molecular theory, relates to the collisions of molecules with the wall.
In continuum thermodynamics, it is a property of the system or surroundings associated with
mechanical equilibrium.
Mechanical equilibrium is attained when pressures of system and surroundings are equal.
Volume – The amount of space occupied by the system.
Amount – The number of moles (could also use mass) in the system.
First Law of Thermodynamics
Work and Heat – Work relates to motion against a force, and involves organized motion of molecules.
Heat relates to random, thermal motion of molecules.
First Law of Thermodynamics – States that heat and work are both forms of energy and can be
interchanged. In an isolated system, such as the entire universe, the total energy cannot change, but the
distribution between heat and work can change. There are multiple statements of the First Law:
The energy of an isolated system is constant.
The energy of the universe is constant.
The change in energy around a cyclic path is zero.
Mathematically, we can write:
dU =δ q+δ w or ∆U = q + w
∆Uuniverse = 0 ∮ dU =0

Expansion (PV) Work – Defined mathematically as δ w=−P ex dV

The work is readily evaluated for certain specialized processes:
Free expansion (Pex = 0) w=0
Constant volume process (∆V = 0) w=0
Constant external pressure w = –Pex ∆V
Vf T
Reversible process (Pgas = Pex) of ideal gas w=−nR∫V dV
i V
Vf
Reversible isothermal process of ideal gas (dT = 0) w=−nRT ln
Vi

Graphical Representation of Work – If the path is plotted on a P-V plot, then the work is the negative
of the area under the curve defining the path. Such a plot is called an “indicator diagram”. The
reversible path between initial and final states produces the greatest amount of work.
Enthalpy – The enthalpy is defined as H ≡U + P V

The constant pressure heat capacity is C P≡ ( ∂∂ HT )

P

Heat Calculations – We can readily evaluate the heat for most of the processes we have just
considered. For the internal energy as a function of temperature and volume, U(T, V), we can write

dU =  
∂U
∂T V
dT   
∂U
∂V T
dV
The constant volume heat capacity is CV≡ ( ∂∂ UT ) V

We know that for an ideal gas  

∂U
∂V T
=0 . This let's us write  U =C V  T

for any process involving an ideal gas. (Recall that CV is a constant for an ideal gas.)
Likewise, for the enthalpy change for an ideal gas we can write  H =C p  T
The heat is readily evaluated for certain specialized processes:
Free expansion, ideal gas (Pex = 0) q = ∆U = CV∆T
Constant volume process, ideal gas (∆V = 0) q = ∆U = CV∆T
Constant pressure process, ideal gas (∆P = 0) q = ∆H = Cp∆T
Adiabatic process q=0
Vf
Reversible isothermal process of ideal gas (∆T = 0) q=nRT ln
Vi
Heat Capacities – For an ideal gas CP – CV = nR
In general, C P −C V =T V α2 / κ

Standard State – Pure material at the given temperature and 1 bar pressure.

Hess's Law  r H o= ∑   f H o− ∑ f Ho

products reactants

T2
Δ r H (T 2)=Δ r H (T 1 )+∫T Δ r C P dT
o o o
Kirchoff's Law
1

where Δ r C oP = ∑ ν C oP , m− ∑ νC oP , m
products reactants

Second and Third Laws of Thermodynamics

Spontaneous Processes – Some processes are observed to occur spontaneously. The Second Law is
required to explain this phenomenon. The Second Law also tells us how internal energy can be
partitioned and how work and heat can be interchanged.
Entropy – A state function that relates to the disorder of the system. Mathematically defined as
δ q rev
dS≡
T
Statements of Second Law
The entropy of the universe never decreases.
A cyclic process cannot be used to convert heat completely into work.
 Heat only flows from a hot body to a cold body.
Mathematical definitions of entropy can be written as
Δ S universe =Δ S system +Δ S surroundings ⩾0
q
∮ dS =0 dS 
T
These last two expressions apply to the entropy of the system.
The entropy change is readily evaluated for certain specialized processes
Vf
Reversible isothermal process of ideal gas (dT = 0)  S sys =nR ln
Vi
 trs H
Phase transition at normal transition temperature  trs S =
T trs
(Note: A phase transition is only a reversible process at the normal transition temperature.)
Reversible adiabatic process (q = 0) ∆Ssys = 0
(Note: This only applies for a reversible adiabatic process. For an irreversible adiabatic process
∆Ssys > 0; the process is spontaneous.)

Adiabatic Equations of State – The following hold for a reversible adiabatic ideal gas
CV CV CP CP CP
V2T R
=V 1 T R R
P 1 T =P 2 T R P 2 V 2γ= P 1 V 1γ where γ=
2 1 2 1 CV

Reversible Engine (Carnot Cycle) – One example of a reversible cycle for a heat engine.
∣w∣ T
The efficiency is = =1− lo
qhi T hi
Statistical Definition of Entropy – The Boltzmann distribution is written as
− / k T
ni e i

= e−ϵ /k T
i

N ∑ e− / k T i or Pi=
q
i

The Boltzmann definition of entropy where W is the weight of the configuration

N!
S = k ln W with W=
n o ! n1 ! n2 ! n 3 ! . ..
Third Law of Thermodynamics – At T = 0, the entropy of a pure crystal is zero.
o
S 0=0
Real materials often have residual entropy, even at T = 0. At any other T, S° is calculated from heat
capacity data up to the temperature of interest.
Entropy Change of Reaction
 r S o= ∑  S om− ∑  S om
products reactants

Fundamental Equation, Legendre Transforms, Maxwell Relations

Fundamental Equation of Thermodynamics dU = T dS – P dV
Legendre Transforms: Allow us to change the independent and dependent variables. Examples of
Legendre transforms are enthalpy and the Helmholtz and Gibbs energies. Their definitions and
corresponding fundamental equations follow:
Enthalpy H = U + PV dH = T dS + V dP
Helmholtz energy A = U – TS dA = –S dT – P dV
Gibbs energy G = H – TS dG = –S dT + V dP
Maxwell Relations: Based on the fact that thermodynamic functions are exact differentials, we can
find relations between different state variables. If df is an exact differential of the form
df = g dx + h dy

then the following relation is true    

∂g
=
∂h
∂y x ∂x y

If there are more than two variables, a similar relation can be written for any two terms, holding the
other independent variables constant. Differentials of all state functions are exact.

Criteria for Spontaneity and Equilibrium

For any spontaneous process, ∆Suniv > 0 must be true. At equilibrium, ∆Suniv = 0.

In terms of the system, we have the following:

dUS,V ≤ 0 dHS,P ≤ 0 dAT,V ≤ 0 dGT,P ≤ 0
For a spontaneous process, the inequality is true. At equilibrium we use the equality.
For an isothermal process, the Helmholtz energy gives the maximum possible pressure-volume work.
For a process at constant temperature and pressure, the Gibbs energy gives the maximum non-PV work.
Standard Reaction Gibbs Energy
 r G o= ∑   f G o− ∑   f Go
products reactants

At a constant temperature, we can also write  r G o = r H o −T  r S o

Properties of Gibbs Energy

Variation with temperature ( ∂∂GT ) =−S

P

This leads us to the Gibbs-Helmholtz equation ( ∂ T ) =−H

∂ (G /T )
T P
2

Or for a total process ( ∂ (Δ G/T )

∂T P
= )
−Δ H
T2

Variation with pressure ( ∂∂GP ) =V

T

P
For an ideal gas, this gives us G m (P )=G om + RT ln
Po
P° is the standard pressure, often 1 atm or 1 bar.
f
For a real gas, we define the fugacity as follows G m (P )=G om + RT ln
Po
f f P Z −1
where lim =1 ϕ= ln ϕ=∫0 dP
P →0 P P P

Chemical Potential

Chemical potential is defined as μ i≡

( )
∂G
∂ ni T , P , n j ≠i

For one component, the chemical potential is equal to the molar Gibbs energy.
The conditions for spontaneity and equilibrium defined in terms of chemical potential are   

where α and β are different states. α is the thermodynamically preferred state in the inequality.

One-Component Phase Diagrams

A graphical representation of the thermodynamically favored state at a given temperature and pressure
condition. The stable phase is the one with the lower chemical potential at the prevailing conditions.
At equilibrium, the chemical potentials of the two phases are equal.
μ α (P , T )=μβ (P ,T ) and d μα (P , T )=d μβ (P ,T ) which gives
−S m, α dT +V m , α dP=−S m , β dT +V m ,β dP or

dP Δ trs S dP Δ trs H
= or =
dT Δ trs V dT T Δ trs V
This is the Clapeyron equation and holds for any first order phase transition.
 Δ fus H
In the limit of small temperature changes, we can write P≈ P ' + (T −T ' )
T ' Δ fus V
If one of the phases is a gas, and we treat the gas as ideal, we can write the Clausius-Clapeyron

1 dP d ln P Δ vap H
equation = =
P dT dT RT2
Again, for small temperature changes, we can integrate this expression to give us
Δ vap H (T −T ∗ )
P
P −Δ vap H 1 1
ln ∗ =
R
−
T T∗
= ( RT T∗ )
Thermodynamics of Mixtures
o P
Mixing of Ideal Gases: For each component before mixing we write μ=μ + RT ln .
Po
o
The total Gibbs energy before mixing is G i =n A μ A+n B μ B=n A μ A+ RT ln ( P
P o ) ( P
+n B μ oB + RT ln o
P )
After mixing, the Gibbs energy is
(
G f =n A μ oA+ RT ln
PA
P o ) (
+n B μoB + RT ln
PB
Po )
PA P
Therefore, the ∆mixG is Δ mix G=n A RT ln +n B RT ln B
P P
Using Dalton's law of partial pressures,
 mix G=n A RT ln x An B RT ln x B=nRT  x A ln x Ax B ln x B 

In general  mix G=RT ∑ n i ln x i=nRT ∑ xi ln x i

i i

For entropy, we have  mix S =−R ∑ ni ln x i =−nR ∑ x i ln x i

i i

For enthalpy and volume of a mixture of ideal gases, we have ∆mixH = 0 ∆mixV = 0
Everything here holds for any ideal mixture. (Note, the two gases were each at the same pressure as
the final mixture in deriving this particular expression.)
Standard States: For gases, we have used the standard pressure of 1 bar or 1 atm. We can instead use
the pressure of the pure gas at the prevailing pressure of the mixture and write
∗ Pi ∗
μ i=μi + RT ln or  i= i RT ln x i
P tot
The second expression can be taken as the definition of an ideal mixture.

Fundamental Equation of Chemical Thermodynamics: dG =−S dT +V dP + ∑ μi dn i

i
Ideal Solutions: For any liquid mixture, there exists a vapor above that mixture. Because the
chemical potential of the vapor must equal that of the liquid, we can discuss the liquid composition in

∗ o P ∗A
terms of the vapor phase. For a pure liquid, we have μ =μ + RT ln
A A
Po
o PA
For a liquid component of a mixture, we have μ A=μ A + RT ln
Po
∗ PA
We can use the pure liquid as the standard state and write μ A=μ A + RT ln
P ∗A
where PA* is the vapor pressure of the pure liquid.
Earlier, we defined an ideal mixture with the relation  i= ∗i RT ln x i
PA
This leads us to Raoult's Law =xA or PA = xA PA*
P ∗A
Raoult's law is best used to describe the solvent in a dilute mixture.
The Raoult's law standard state is the pure liquid component.

Ideal Dilute Solutions: For the solute in a dilute mixture, the vapor pressure of the solute is
proportional to the mole fraction, but the constant of proportionality is not the vapor pressure of the
pure component but an empirically determined constant. P B = x B KB
This is known as Henry's law. It is readily shown that if the solute obeys Henry's law, then the solvent
must obey Raoult's law.

The Henry's law standard state is the hypothetical pure component with a vapor pressure of KB.

Colligative Properties: The addition of a nonvolatile solute to a liquid results in a lowering of the
chemical potential of the solution. This leads to boiling point elevation and freezing point depression.
We need to equate the chemical potential of the solution with that of the pure vapor or solid.
Freezing Point Depression and Boiling Point Elevation – For dilute solutions, the freezing point
decreases and boiling point increases relative to the pure solvent.
Osmosis – When a solution is separated from a pure solvent by a semipermeable membrane, solvent
will flow into the solution. This means that a greater pressure must be applied to the solution than to
the solvent to keep the system at equilibrium. This osmotic pressure ∏ can be modeled by the van 't
Hoff equation RT n J =V or =RT [ J ] where [J] is the molar concentration of solute.
If the solution behaves non-ideally, we can use =[ J ] RT  1B [ J ]C [ J ]2.. .  where B, C, etc.
are constants.

Activity
To account for the non-ideal behavior of real gases, we defined a quantity called the fugacity to serve
as an effective pressure. Likewise, we need to account for non-ideal behavior of solutions. We will
define an effective concentration called the activity. Let's first consider the activity of the solvent.

Solvent Activity: For a solvent that obeys Raoult's law, we would write
∗ ∗ PA
μ A=μ A + RT ln x A=μ A + RT ln
P ∗A
For a real gas, we need to use the fugacity and not the pressure. This gives us
∗ fA
μ A=μ A + RT ln
P ∗A
fA ∗
We define the activity as a A= which gives us  A= A RT ln a A
P ∗A
aA
In terms of the liquid composition, we can write lim =1
x A 1 xA
aA
and we define the activity coefficient as  A=
xA
Our standard state is the pure solvent, so the activity becomes equal to the mole fraction and the
activity coefficient goes to 1.

Solute Activity: If we take as our standard state as the hypothetical pure liquid with a vapor pressure
equal to the Henry's law constant, we write the following
 B = oB RT ln x B note the superscript o compared to the * before.
To account for deviations from ideality, we again use an activity and write
fB
 B = oB RT ln a B where the activity is defined aB=
KB
aB aB
We also write lim =1 and define the activity coefficient as  B=
x B 0 xB xB
Use of Molality – Sometimes it is more convenient to use a standard state of a 1 molal solution. In this
bB
case, we write μ B =μ oB + RT ln a B with a B = B
b oB
These activity coefficients have to be determined empirically.
Note: the Henry's law and 1 molal standard states are often used to describe the solute.
Ionic Standard State: The standard state for ionic solutions is generally taken to be a solution of
ci
1 molar concentration. ai = i
c oi
Biological Standard State: The standard state for biological systems is generally taken to be a pH of
7, not the pH of 0 that is normally used for ionic solutions.
Summary of Activities: We need to properly define activities for a variety of materials.
Pi fi
Ideal Gas – ai (ideal gas)= o
Real Gas – ai ( real gas)=
P Po
Liquid Mixture – In a liquid mixture, we simply use the activity with either the Raoult's law or Henry's
law standard state. We can also use a standard state of 1 molal or 1 molar concentration.
fi fi ci
a i  RLSS = ∗
= RL
i xi ai  HLSS = = iHL x i ai concentration= i
f i
Ki co
f p
Pure Liquid or Solid – a i  pure liquid /solid = o (Often has a numerical value close to 1.)
f
NOTE: The choice of standard state cannot affect the results of a calculation for a particular process.

Chemical Equilibrium
n J −n J , o
Extent of Reaction: Denoted by the symbol  . Defined as =
J
An infinitesimal change is denoted d  .
Reaction Gibbs Energy: In general a chemical equation can be written in the form ∑  J J =0
J
where J denotes the species and  J is the stoichiometric coefficient. The convention on the sign of
 J is that the sign is positive for products and negative for reactants.
The change in number of moles of each species is given by dn J = J d 

The general definition of the reaction Gibbs energy is Δ r G= ( ∂G

∂ξ ) T,P
=∑ νJ μ J
J

If ∆rG < 0, the forward reaction is spontaneous, and is called exergonic.

If ∆rG > 0, the backward reaction is spontaneous, and is called endergonic.
If ∆rG = 0, the reaction is at equilibrium.
Reaction Quotients and Equilibrium Constants: We can express the chemical potentials in terms of
o
activities for each product and reactant as  J = J RT ln a J
Δ r G=Δ r G o + RT ln ∏ a J =Δ r G o + RT ln Q
νJ
This leads to the expression
J

Q =∏ a J
J
Q is the reaction quotient
J

If the reaction is at equilibrium, then ∆rG = 0 and we have Δ r G o=−RT ln K

K is the equilibrium constant, and is constructed from the activities in the same manner as Q. The
activities are those of the equilibrium mixture.
Changes of Equilibrium with Conditions: Changing the conditions can often change the equilibrium
composition for a given reaction.

Addition of Inert Gas – Because ∆rG° is defined at standard pressure, ( ∂∂ KP ) =0

T
. Addition of inert

gas doesn't change the equilibrium composition if gases are ideal. Composition will change for real
gases, because of changes in fugacity coefficients. K still does not change.
Compression of Reaction Vessel – Changing the volume of the reaction vessel may cause the partial
pressures to change, but the equilibrium constant does not change. If the pressure is increasing, the
composition will shift to favor the side with the fewer number of moles of gas. This is an examples of
Le Chatelier's principle.
Changes of Temperature – Taking the derivative of the relation between ∆rG° and K and using the
Gibbs-Helmholtz equation gives us the van 't Hoff equation
o o
d ln K  r H d ln K − r H
= or =
dT RT2 d 1/T  R
The value of K does change with temperature.
Change of Composition – The equilibrium composition will depend on the initial conditions and will
change if additional product and/or reactant are added to the system. The ratio defined by K will
always stay the same, however, if the temperature remains the same.
Molecular Aspects of Bonding and Equilibrium: Formation of a chemical bond always results in a
decrease in enthalpy; ∆H < 0 for bond formation. Entropy of this system also decreases. Bond
formation is only spontaneous if the stabilization is greater than the entropy cost, given by T ∆S. In
other words, bond formation is only spontaneous if ∆G = ∆H – T ∆S < 0.
Things You Must Know
First Law of Thermodynamics dU = q w
Definition of mechanical work δw =−P ex dV
Definition of reversible process P ex =P
Definition of enthalpy H ≡U + P V

Definitions of heat capacity CV ≡   ∂U

∂T V
C P≡( ∂∂HT )
P

Internal energy (and enthalpy) of ideal gas only depend on T, therefore dU = CV dT

 q rev
Definition of entropy dS ≡
T
Second Law of Thermodynamics  S universe = S system  S surroundings 0
Definition of adiabatic process δ q=0 or q = 0
Definitions of Helmholtz and Gibbs energy A = U – TS G = H – TS

Definition of chemical potential μ i≡

( ∂∂ Gn )
i T , P , n j ≠i

Expressions for activity

Dependence of chemical potential on activity μ i =μ oi + RT ln a i
Gibbs energy of reaction under nonstandard conditions Δ r G=Δ r G o + RT ln Q
Q =∏ a J
νJ
where
J

o
Relationship between ∆rG° and K  r G =−RT ln K

Things That are Good to Know

The 4 Gibbs equations dU = T dS – P dV dH = T dS + V dP
dA = –S dT – P dV dG = –S dT + V dP
How to derive the 4 Maxwell relations. (Don't try to memorize them!)
Gibbs energy in terms of enthalpy and entropy, isothermal process ∆G = ∆H – T ∆S

Fundamental equation of chemical thermodynamics dG =−S dT +V dP + ∑ μi dn i

i