PhysChem Filled in

CET 1 (convergence):
Physical Chemistry
Michaelmas Term 2010
Dr. C. Kaminski
E-mail: cfk23@cam.ac.uk
http://laser.ceb.cam.ac.uk
CFK, Phys Chem. I (convergence)

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Course Outline
The course is for the group of students who join the department through the
engineering route. Physical chemistry is of central importance in most aspects
chemical engineering. The aim is to build the foundations of chemical
thermodynamics and chemical kinetics, crucial background for many of the
other courses to be taught in this department.
You will have already encountered thermodynamics, so certain concepts should
not be unfamiliar; but we approach these ideas from a new angle: here we use
thermodynamics to predict whether a given chemical reaction will occur or not.
Following on from this, we use the concepts provided by chemical kinetics
theory to tell us how fast a reaction will happen.
All of the information you require for this course is contained within the printed
lecture notes; nevertheless, you may well find it useful at times to consult one of
the textbooks listed in the relevant section of the Syllabus Document.

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Part A:
Thermodynamics of Chemical Reactions
1 Introduction
We want to answer the questions:
o How much energy will be
consumed or released
during the reaction?

o Is a particular chemical reaction energetically favourable?
o Thus:
Will a particular chemical reaction happen
Will a particular reagent be completely
at all?
consumed
by the reaction, or will only partial conversion

occur?
Chemical thermodynamics answers these questions.

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2 Definitions and Assumptions

2.1 Functions of two variables
The thermodynamic state of a 1 mol of any pure gas may be defined
by specifying T, and p. For example,
underbar to denote a
as
molar quantity (
. We use the
in m3 mol-1), known
specific volume.
This relationship is shown graphically on the 3D diagram below.

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partial derivatives
At any point on the diagram, we may define
with respect to T and p. This allows us to write the total
differential
2.2 Ideal Gas Law

In this lecture course, the assumption of ideal gas behaviour will be
made throughout. i.e.:
Ideal gas behaviour is based on assumption that:

gas molecules have negligible volume
forces of attraction / repulsion
between molecules are
insignificant
The ideal gas law tends to give reasonable results at low or ambient
pressure, but gives less accurate predictions at higher pressure since
molecules are forced closer together, thus interacting more strongly.
2.3 Internal Energy
Important consequence of the second of these ideal gas assumptions:
If there are no energy interactions between molecules then
Internal Energy
Specific
( U ) depends only on energy states of individual
atoms.

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Therefore, internal energy is a function only of temperature. i.e.:
2.4 System and surroundings
System: what we are interested in, i.e. the species undergoing

reactions
Surroundings: what the system is interacts with, i.e. beaker,

bench... the universe

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It may seem strange we have to consider the
universe when
looking at questions such as: how much product is produced by the

reactions in the beaker? But it turns out that such processes are
governed by the principle that a quantity called
entropy must
increase in the universe as a result of the reactions.
2.5 State functions and path functions
Different paths may be followed in going from state 1 to state 2.

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state function is a variable that depends only on the present
condition of the gas. It is independent of the route the gas followed

to arrive in that state; examples are p, V, T, U etc.
Changes is such property between a state 1 and a state 2 (see
diagram) are path independent; e.g. a change in specific volume:
For a
path function this is not the case, e.g. heating a system
(heat input = dQ) is path dependent. The quantity of heat energy

entering the system cannot be determined merely by examining the
initial and final states.
For these reasons, state functions can be classified as exact
differentials, and path functions as inexact differentials

2.6 Intensive and Extensive Properties
Intensive properties: independent of size of system (e.g. p, T, V,

). They are often functions of two variables, e.g.
Extensive properties: depend on size of system (e.g. V, U), and

are typically functions of at least three variables, e.g. V = f (T, p, n).

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2.7 Relations between partial derivatives

There are a few useful tricks for manipulating partial derivatives of
functions of two variables. These are introduced here for use later.
A. The order in which partial derivatives are taken is of no
consequence:
B. Triple
Product
If the total differential of a function is constant (e.g. dV = 0) we may
write:
Rearranging, and introducing partial derivative notation, this
becomes:

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C. Partial derivatives with the same variable held constant may be
manipulated like fractions

(i)
(ii)
, where f is a function of T and p.
D. A derivative may be formed from the total differential

i.e. from
we obtain
Worked Example 1
(i) Confirm, for an ideal gas, that:
(ii) Confirm, for an ideal gas that:
(iii) Confirm, for an ideal gas that:

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3 The 1st law of thermodynamics

The total energy of a system (in all its forms) is conserved.
For instance, mechanical work can be completely converted into
heat energy.
Consider a
closed system (= a system that has no material
entering or leaving, but energy can be added/lost).

o 1st law implies that dU = dQ + dw
dU = change in specific internal energy of the

system
dQ = heat
added to system
dw = total
work done on the system
o If the volume of the system increases by an amount dV,

then work done by the system on the surrounding: this socalled expansion work or p-V work.
This is given by:
Expansion Work = pdV

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o Other work terms (e.g. electrical work to drive a current
through a circuit, or work to rotate a turbine blade) are

termed shaft work
For a closed system with no shaft work:
o The 1st law may be written as:
dU = dQ pdV
constant volume we have: dU = dQ
o At
i.e. in this case change in internal energy is the heat

added to the system
o At constant pressure we have: dU + pdV = dQ
Define enthalpy H = U + pV
Thus in this case dH
= dQ
i.e. in this case change in enthalpy of the system is

the heat added to the system
We tend to use Internal Energy ( U ) when considering constant
volume systems, and Enthalpy ( H ) when considering constant
pressure systems.

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In order to answer the question how much (heat) energy will
be absorbed or released during a chemical reaction?

we thus need to know about U and H.
4 Heat capacities
We would like to know how U and H vary with temperature. We
have seen that for an ideal gas, U is solely a function of T:
Constant volume
specific heat capacity:
For constant pressure systems, we work with H rather than U.
= 0 for ideal gas
Constant pressure
specific heat capacity:

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Heat capacities have units J mol1 K1 (note that they are also often
quoted in mass units J kg1 K1).
The heat capacities enable changes in U and H to be obtained for a
system in which no chemical reaction occurs:
and
o (Aside: for non-ideal gases, U and H also vary with
pressure. Expressions for (U/p)T and (H/p)T will be
derived in process calculations lecture course with Dr
Barrie.)
Note that Cp and CV are
not constants
for a particular
substance. They can increase significantly with temperature.

Special case: an ideal gas obeys
An ideal gas also has Cp and CV
Cp = CV + R
independent of pressure
(They may vary slightly with pressure for non-ideal gases).

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4.1
Estimation of CP and CV
Heat absorbed by a system goes into increasing the molecular

motions:
o
translational modes:
there are 3 such modes for a
3-dimensional system. It can be shown that each

translational mode contributes R/2 to CV.
o
rotational modes:
0 of these for a single atom; 2 of
these for a linear molecule (e.g. CO, O2 etc.); 3 of these

for a non-linear molecule (e.g. H2O, CH4 etc.). It can be
shown that each rotational mode can contribute up to R/2
to CV.
o vibrational modes:
3N5 of these for a linear
molecule; 3N6 of these for a non-linear molecule (where

N is number of atoms in the molecule). It can be shown
that each vibrational mode can contribute up to R to CV.

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For molecules in a gas:

o At room temperature:
all translational and rotational
modes are normally excited, while the vibrational modes

are negligible.
o Below room temperature: rotational modes wont be fully
excited
o Above room temperature: vibrational modes become
excited as T is increased
Hence rough estimates of CV and CP at room temperature are:
o Monatomic gas (e.g. Ar): CV = 1.5R, CP = 2.5R
o Diatomic gas (e.g. N2) CV = 2.5R, CP = 3.5R
o Non-linear triatomic gas (e.g. H2O): CV = 3R, CP = 4R
In practical situations we often express the temperature
dependence of the heat capacity as a polynomial:
o Cp = a + bT + cT 2 + dT 3
o The parameters a, b, c and d that apply at low pressure are
derived from experimental data
and may be
looked up in reference books.

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o Sometimes alternative expressions such as Cp = a + bT +

c/T 2 are used.
5 Energy changes during a chemical reaction

Different chemical species have different internal energies and
enthalpies because they
contain bonds of different strengths.
There will therefore be a change in internal energy and enthalpy

when a chemical reaction takes place.
o Ureaction = U(products) U(reactants)
o Hreaction = H(products) H(reactants)
For reaction in a fixed volume system (with no shaft work) heat

will need to be added/removed depending on whether Ureaction is
positive or negative
For the more common case of a reaction in
system
a constant pressure
(with no shaft work), heat will need to be
added/removed depending on whether Hreaction is positive

(implying an endothermic reaction) or negative (as in an
exothermic reaction).

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5.1 Evaluation of enthalpies of reaction

We want to calculate Hreaction = H(products) H(reactants)
But what is H for a particular chemical? There is
as absolute enthalpy;
no such thing
we can only measure changes in
enthalpy.
Special case: if no chemical reaction is occurring we can specify a
particular reference T and p at which we take H to be zero (e.g.
steam tables take H = 0 for liquid water at its triple point), and
calculate H at all other conditions on this basis.
If chemical reaction takes place, we need to allow for the fact that
the different species present will have different enthalpies even at
the same T and p.
Documented in reference books are
of formation, H f 0
standard molar enthalpies
, of chemical species:
o This is the enthalpy change upon the formation of one mole

of the compound from its constituent elements (with all
species in their most stable form at 1 bar pressure and the
temperature specified).
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o standard implies the pressure is 1 bar. It is denoted by the
superscript 0. It does not indicate any particular temperature.

Values are commonly given at 298 K in reference books, but
they could equally well be given at any other temperature.
o Note that elements in their most stable form at 1 bar and
the T specified will have H f 0 = 0
For instance, H f 0 (298 K) = zero for

molecules of O2 gas; atoms of Ar gas; atoms of
Hg liquid.
We now recognise that the enthalpy of reaction can be written:
Hreaction = Hf(products) Hf(reactants)
Hence the standard molar enthalpy of a reaction will be:

H 0(T) =
i (H f 0)i
where i denotes the chemicals involved, and i are the
stoichiometric coefficients
of the reaction.

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o For example the reaction A + 2B 3C has

H 0 = 3H f 0(C) H f 0(A) 2H f 0(B) at the
temperature indicated. Here H 0 has an underbar: it is per
mole of A reacted; per 2 moles of B reacted etc.
Note that we can actually
measure H f 0 values:
o For instance, H f 0 (CO2(g), 298 K) is the heat absorbed

by the reaction C(s) + O2(g) CO2(g) at 1 bar and 298 K.
Its ve because this reaction
releases heat
o Other H f 0 values can be obtained indirectly by using
Hesss law:
overall enthalpy change for a particular
reaction is the same regardless of route.

o For instance:
H f 0 (CH4(g)) can be obtained from knowledge of
H 0 for the reactions C + O2 CO2, 2H2 + O2
2H2O and CH4 + 2O2 CO2 + 2H2O.

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5.2
How does Hreaction vary with T?
We know:
H 0(T) =
i H i0. Hence:
where
at the standard pressure of 1 bar.
Integrating gives us:
Worked Example 2a:

Calculate the enthalpy of reaction for N2(g) + 3H2(g) 2NH3(g) at
450 K using the following crude guesses for the heat capacities:
CP(N2) = 3.5 R, CP(H2) = 3.5 R, CP(NH3) = 4R. It is known that
H f 0(NH3(g), 298 K) = 45.72 kJ/mol

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Worked example 2b
Repeat example 2a but using the heat capacity expressions (giving
giving CP in J/mol.K with T in K):
CP (N2) = 28.67 + 0.00155 T
CP (H2) = 28.25 + 0.00218 T
CP (NH3) = 26.19 + 0.03159 T
(note that a more accurate calculation would include higher order
terms T 2 and T 3)

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Worked Example 2a
H0(298 K) = (2 x 45.72) (1 x 0) (3 x 0) = 91.44 kJ/mol
CP0 = 2CP(NH3) CP(N2) 3CP(H2) 6R = 49.9 J/mol.K
= 91440 49.9(450298) (in J/mol)
Hence H0(450 K) 99.02 kJ/mol

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Worked Example 2b
As before, H0(298 K) = 91.44 kJ/mol
o CP0 = 2CP(NH3) CP(N2) 3CP(H2) = 61.04 + 0.05509 T
o (Aside: this means CP0 = 44.6 at 298 K and 36.2 at 450 K)
H0(450 K) = 91440 61.04 x (450298) + 0.05509 x (45022982)/2

Hence H0(450 K) = 97.59 kJ/mol

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5.3 Other useful enthalpies

It is common to find the following
latent heat
enthalpy
values in reference books:

o Enthalpy of vaporisation:
H vap, is the enthalpy change for A(l) A(g)
o Enthalpy of fusion:
H fus is the enthalpy change for A(s) A(l)
(N.B. its badly named: it should be called the
enthalpy of melting; the definition is such that H fus
is always a positive quantity)
o Enthalpy of sublimation:
H sub is the enthalpy change for A(s) A(g)
It is also common to find
enthalpies of combustion
in reference books.
o H c is the enthalpy change for complete combustion in
oxygen of one mole of the chemical specified.

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6 Entropy and the 2nd law of thermodynamics

The previous section has answered the question how much energy
is released/absorbed during a chemical reaction, but hasnt
answered the more fundamental question of whether it is
thermodynamically favourable for the reaction to take place.
o Clearly overall change in enthalpy is not the overriding
factor;
both exothermic and endothermic reactions
can take place spontaneously

o Similarly overall change in internal energy is not the
overriding factor.
The 2nd law of thermodynamics part 1: there exists a state function
called entropy, S.
o Entropy is mathematically related to the degree of
molecular disorder
of a system
Denote the standard molar entropy of a substance at

1 bar as S 0 (and specify the temperature).

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For a particular substance (e.g. water), we expect S 0

to increase in the order
solid liquid gas by
the molecular disorder argument.

In the same way that different chemical species have different
enthalpies and internal energies, they also have different entropies.
Thus for a chemical reaction:
o Sreaction = S(products) S(reactants)
o S 0(T) =
i (S 0)i
o For example, the reaction A + 2B 3C has

S 0 = 3S 0(C) S 0(A) 2S 0(B) at the temperature
indicated.
The 2nd law of thermodynamics part 2: the entropy increase of a
closed system when heat dQ is added
reversibly
to a
system at temperature T is dQ/T.

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Consider the condensation of water:
This process occurs reversibly if the temperature difference

between system and surroundings (dT) is infinitesimally small.
Therefore, the driving force for heat transfer is miniscule, and the
process occurs infinitely slowly. It is infinitely close to
equilibrium.
A tiny change in the temperature of the surroundings would cause
the water to evaporate instead of condense. Hence, reversible.
For reversible processes only, the system would return to its
original conditions (T, p, V, U, H, S, etc.) if the same amount of
heat was subsequently removed.
Any process involving a temperature difference or mixing of

different species will not be reversible. i.e. no real process is
reversible

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The 2nd law of thermodynamics Part 3: for a reversible process,

the change in entropy of the universe is: dSuniv = 0
(Remember: the universe = the system plus its surroundings)
Key point: For all spontaneous (i.e. natural, irreversible) processes,

the entropy of the universe must increase:
dSuniv > 0
o Consider pure ideal gas A being mixed with pure ideal gas B:
There is no change in the internal energy of the
system, nor in the enthalpy of the system; this is

because ideal gas molecules have
negligible
interaction with each other.

There is an increase in the
randomness
(and
thus entropy) of the system due to mixing.

Thus, the fact that gases will spontaneously mix can
be explained by entropy and the 2nd law.

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In the general case for a closed system, we can write

dSsys dQsys/Tsys
where: > applies for irreversible (natural) processes
= applies only for reversible processes
The total entropy change may be written as:
Since the surroundings are large compared to the system, Tsurr is

unchanged by energy exchange with the system. Furthermore,
since any energy exchange is small compared to the total energy of
the surroundings, the heat exchange is reversible from the point of
view of the surroundings.
dSsurr = dQsurr/Tsurr
The the heat received by the surroundings from the system is given
by: dQsurr = -dQsys
If we make the assumption that the system and surroundings
are at the same temperature, we may write.

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We must evaluate dSuniv to determine in which direction a process

will take place. It may not have escaped your notice that this
would be somewhat tricky to achieve in practice! However, we
will soon use this idea to develop a more useful criterion.
6.1 Variation of entropy with temperature

We would like to be able calculate how S and S 0 vary with
temperature.
Consider a closed system with no non-expansion work:
dU = dQ pdV
If heat is added reversibly, then dQ = TdS and so
dU = TdS pdV
In fact dU = TdS PdV is true even if heat isnt added reversibly
because its a relationship between state functions, and so route
doesnt matter.
Now dH = dU + pdV + Vdp from definition of H, and so
dH = TdS + Vdp
Hence
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Now
Hence
Hence
Hence
6.2 Measurements of entropies

The concept of
absolute entropy
exists (unlike the
situation for enthalpy where only changes in enthalpy have any

physical meaning).
The 3rd law of thermodynamics states that the entropy of a perfect
crystal at T = 0 K is zero; absolute entropies can therefore in
principle be calculated on this basis.

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Area under graph of Cp(T)/T from 0 to T gives S(T)
If there is a phase change (pc) then at Tpc , Cp goes to infinity:
To acccount for this discontinuity, extra entropy change on

phase change needs to be included:

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Difficult in practice to measure heat capacities down to 0 K. This

has been done for some substances but usually not necessary since
were more interested in entropy changes rather than absolute
entropies. Thus more convenient reference states may be defined
to which measured entropies can be related, in the same way as we
have already done for enthalpy.
Worked Example 3
Calculate the standard entropy change for the reaction for N2(g) +
3H2(g) 2NH3(g) at 450 K using the data given in Worked Example
2 and the following standard entropy values at 298 K: S0(N2) = 191.6,
S0(H2) = 130.7, S0(NH3) = 192.5 J/mol.K.

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Answer:
S0(298 K) = (2 x 192.5) (1 x 191.6) (3 x 130.7) = 198.7 J/mol.K
Recall CP0 = 61.04 + 0.05509 T for this reaction from the previous
example
S0(450 K) = 198.75 61.04 ln(450/298) + 0.05509 (450298)

Hence S0(450 K) = 215.5 J/mol.K

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7 Gibbs free energy

Previously we found that reactions take place if the entropy of the
universe (rather than just the system) increases. i.e. Suniv > 0
o However, its difficult to deal with the entire universe. Its
easier to deal with just our system (e.g. we often know the
T and p of our system). We therefore would like to derive
an expression equivalent to the 2nd law statement that we
can apply to our system.
7.1 Gibbs energies

We now define a state function called Gibbs Energy (G). We have
seen that some energy will always be wasted in generating an increase
in entropy. Evaluating G for a particular reaction tells us whether
there is any energy left over to make the reaction proceed.
G = H - TS
hence: dG
= dH - TdS SdT
For constant temperature, this becomes: dG
= dH TdS
(Very important equation!)

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If pressure is also constant, we may write:
The term on the left may be recognised as dSuniverse! (assuming Tsys

= Tsurr)
Thus for a closed system, reactions with dGsys negative will be

spontaneous because this increases the entropy of the universe.
In the case that dGsys = 0, then G of the system will be at a
minimum, S of the universe will be at a maximum, and the system

will have reached equilibrium
7.2 The master equations

We saw last time that for a closed system with no shaft work, we
may combine the 1st and 2nd Laws to give:
dU = TdS pdV
This is called the first master equation, and it applies even if heat
isnt added reversibly (it is a relationship between state functions)

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We also saw last time that:
dH=TdS+Vdp
This is called the second master equation
We have just seen that: dG = dH - TdS SdT
By substituting for dH, form a third master equation:
dG = Vdp SdT
Note that the master equations hold for ANY system change,
reversible or irreversible, since they only involve state functions.
7.3
Evaluating Greaction at a specified T
Note that, as was the case for enthalpy, there is no such thing as
absolute Gibbs free energy: we can only measure (indirectly)
changes in Gibbs free energy.
o Special case: if no chemical reaction is occurring we can
specify a particular reference T and p at which we take G
to be zero (e.g. steam tables take G = 0 for liquid water at
its triple point), and calculate G at all other conditions on
this basis.

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o If chemical reaction takes place, we need to allow for the

fact that the different species present will have different
values of G even at the same T and p.
To get Greaction we can write:
o Greaction = G(products) G(reactants)
o Greaction = Gf(products) Gf(reactants)

o G0(T) =
i (G f )i
o We can look up values of G f 0, the standard Gibbs free

energy of formation, of different species in reference
books.
Alternatively, we may know (or calculate) the enthalpy and
entropy of reaction. In which case:
o at a specified (constant) temperature:
G = H TS
and thus: G 0 = H 0 TS 0

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7.4
How G varies with T
Consider the third master equation: dG
= Vdp SdT
Hence:
While this expression is useful, we often develop it further when
interested in how Greaction varies with T.
G = H TS implies: S = (G H)/T
By considering the quotient rule, this becomes:
This is sometimes called the Gibbs-Helmholtz equation.

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Worked Example 4
Calculate the standard Gibbs free energy change for the reaction for N2(g) + 3H2(g)
2NH3(g) at 298 K and 450 K using the information in previous examples.
Answer:
Weve already found:
H0(298 K) = 91.44 kJ/mol;
H0(450 K) = 97.59 kJ/mol
S0(298 K) = 198.7 J/mol.K;
S0(450 K) = 215.5 J/mol.K
Hence G0(298 K) = 91440 298(198.7) = 32.23 kJ/mol

and G0(450 K) = 97590 450(215.5) = 0.62 kJ/mol

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8 Ideal Mixtures
8.1 Mixing of ideal gases
Why do gases mix spontaneously?
Gibbs free energy of the mixture must be lower than that of the
separated gases for this to occur.
Consider ideal gases A and B, both at pressure p:
In a mixture of gases, the partial pressure of each species is
expressed as:
pi=xi p
where xi is the mole fraction:
CFK, Phys Chem. I (convergence),
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before mixing:
pA = p = pB
after mixing:
Thus, after mixing, both pA and pB are less than p.

At constant temperature: dG = Vdp=
It is follows that the Gibbs energy varies with p as:
where p0 is the standard pressure (1 bar).

In an
ideal gas
there is no difference in G for a pure gas at
pressure p and the same gas in a mixture at a partial pressure pi = p

because there are no interactions between the molecules in
the mixture.
Hence:

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This is lower than before both for gas A and for gas B and hence
mixing is spontaneous.
The figure above shows how the Gmix varies with xA upon mixing
of two ideal gases A and B.

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8.2 The chemical potential

For mixtures of ideal gases:
G = nA G A(pA) + nBG B(pB) + nCG C(pC) +...
and
For non-ideal gases this no longer holds (species interact!). Gibbs

free energy of species i will depend on type and amount of other
species present. To take into account this non-ideality we have to
introduce the chemical potential i for substance i, which is defined
as:
It tells us how G changes as an (infinitesimal) amount dni is added

to the mixture, keeping constant the pressure, temperature and
number of moles of species other than i.
The Gibbs free energy of the mixture can then be evaluated using:
G = nAA + nBB + nCC +...

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In this course, we deal only with ideal gas behaviour, for which we
can say, i = Gi, and hence: i0 = G 0f, i leading to:
where i0 is the
chemical potential
of species i under
standard conditions in its pure form.

It is also worth remembering that for any pure substance, = G,

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9 Equilibrium constants
Most reactions do not proceed to 100% conversion. We will now
introduce the equilibrium constant, which characterises the
relative abundances of reactants and products.

An equilibrium constants refers to a particular reaction at a
specified T; you may have already encountered them in the form Kc
and Kp. e.g. for reaction A + 3B 2C:
o equilibrium constant based on concentration
Kc = [C]2 / [A][B]3 (units here would be concentration2).
o equilibrium constant based on partial pressure
Kp = pC2 / pApB3 (units here would be pressure2).
We shall now learn about a dimensionless thermodynamic
equilibrium constant K that can be predicted using chemical
thermodynamics.

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9.1 General case

Define
o
where ai is the (dimensionless) activity of

species i given by:
for an ideal gas: ai = (pi / 1 bar) where pi is the
partial pressure of species i.

for a pure solid: ai = 1
for a pure liquid: ai = 1
Other situations will be referred to in the Process
Calculations lectures
For example: N2(g) + 3H2(g) 2 NH3(g) has under
ideal gas conditions:
where yi denotes mole fraction of gas i.

Note that the thermodynamic K is always
dimensionless.

Handout number 3
48
9.2 Predicting Equilibrium Composition

Remember that the criterion for predicting whether a particular
chemical reaction will happen is that reactions take place if dG is
negative.
Consider a reversible reaction between species A and species B
(i.e. both forward and back reactions are possible) so that AB
(e.g. isomeric interconversion). In this case:
o if pure A is present then AB has negative dG, so the
forward reaction occurs
o if pure B is present then BA has negative dG, so the
backward reaction occurs
o at a particular concentration of A and B, the dG for
forward and back reaction will be zero (i.e. the species will
be at equilibrium with each other).

Handout number 3
49
o This is illustrated below:
o Depending on the sign of the slope of a point on this graph

the reaction will proceed to produce more products or
reactants. At c the mixture is in equilibrium and there
will be no further change in composition.
o Note that on graph a change from pure reactants to pure
products is not spontaneous as G 0 > 0 for this
conversion: such a reaction therefore favours reactant (and the
equilibrium at c lies to the left of the centre).
o However, it is important to note that the reaction can

convert some of the reactants to product, and the fact that
G 0 > 0 does not imply that the reaction cannot
proceed at all.
Handout number 3
50
To predict equilibrium concentrations, we need to find the

concentrations at which dG = 0. We thus need to know how G of a
reaction mixture varies with concentration
9.3 Derivation of equilibrium constant (gases)

Consider the following reaction, where reactants and products are
all gases:
Notice the underbar. This is the Gibbs Free Energy change per i
moles of component i formed.
Remember that the chemical potential i is defined, for an ideal
gas as being equal to Gibbs Free Energy, so:

Handout number 3
51
Hence:
At equilibrium G = 0, thus:
We recognise the term in brackets to be the dimensionless

equilibrium constant defined above. It follows that:
G 0 = RT ln K
Using G0 = RT ln K we can predict the value of K, at a given T,
from G0 (which we can get using the thermodynamic
relationships discussed earlier)
This formula will hold in a wide range of cases, as long as the
values of activity are appropriately defined.

Handout number 3
52
Worked Example 5
Calculate the thermodynamic equilibrium constant for the reaction for N2(g) +
3H2(g) 2NH3(g) at 298 K and 450 K.
Answer:
We have found previously G0(298 K) = 32.23 kJ/mol and G0(450 K) =
0.62 kJ/mol
G0 = RT ln K implies K = exp(G0/RT)
Hence K(298 K) = 446000 and K(450 K) = 1.18

Handout number 3
53
9.4 Le Chateliers principle

When a system in equilibrium is subjected to a change, the
composition of the equilibrium mixture will alter in such a way as
to counteract that change.

This means that for a mixture of gases initially at equilibrium:
Adding more of a reactant will cause the forward reaction to occur.
Increasing the temperature will cause the reaction to proceed in the
direction in which it is endothermic
Increasing the pressure will cause the reaction to proceed toward
the side that has less moles of gaseous species
After any of these changes, the system will reach a new equilibrium.
9.5
Variation of K with temperature
ln K = G0/RT
Using Gibbs-Helmholtz equation, this gives:
o This is sometimes called the vant Hoff equation

Handout number 3
54
o It implies that K increases with T if H0 is positive

(endothermic); K decreases if H0 is negative (exothermic)
o This is consistent with what we said above:
Endothermic means: T K pproduct
Integrated form of vant Hoff equation:
Worked Example 6
Recalculate the thermodynamic equilibrium constant K at 450 K for
the reaction N2(g) +3H2(g) 2NH3(g), but this time use the vant
Hoff equation.
Answer:
From data in reference books (as in previous examples) have found:
At 298 K:
o H0(298 K) = 91.44 kJ/mol; G0(298 K) = 32.23 kJ/mol

Handout number 3
55
o Hence K (298 K) = 446000

o Also know CP0 = 61.04 + 0.05509 T for this reaction
Key equations:
and
Hence K(450 K) = 1.18
(which obviously agrees with the answer to
Example 5)

Handout number 3
56
9.6
Use of equilibrium constant K
The equilibrium constant enables us to calculate the concentrations

of reactants and products if thermodynamic equilibrium is attained.
o A very high value of K implies conversion can reach

virtually 100%.
o A very low value of K implies conversion is negligible.
o In the general case, we need to calculate the fractional
conversion of reactants.
Example: consider again the reaction: N2(g) +3H2(g) 2NH3(g)
Assume that at the start of the reaction, only N2 and H2 are present
and that they are in stoichiometric proportions. Then:
N2
H2
NH3
Initial moles
Final moles
1x
3 3x
2x
(1 x) / (4 2x)
3(1 x) / (4 2x)
2x / (4 2x)
Final mole fraction
here x denotes the extent of reaction (i.e. number of moles of N2

reacted).

Handout number 3
57
Now
Hence:
Maximum fractional conversion at 298 K and 1 bar pressure:
o we have shown in worked examples that K (298 K) =
446000
o
o solution is x = 0.966 (obtained iteratively)

o have shown in previous examples that K (450 K) = 1.18
o
solution is x = 0.356

o
solution is x = 0.648

Handout number 3
58
9.7 Some points to note

Note that while the value of K is independent of pressure, the
predicted conversion does depend on pressure when the
number of gaseous moles on the left-hand and right-hand

side of the equation differ.
The above examples illustrate Le Chateliers Principle: if a system
at equilibrium is subject to a small change, the equilibrium tends to
shift so as to minimize the effect of the change:
o For N2(g)+ 3H2(g) 2NH3(g)
H0 = ve
o increasing T implies lower conversion (because this is an

exothermic reaction)
o increasing p implies higher conversion when number of
gaseous moles on left-hand side is greater than those on
the right-hand side of equation.

Handout number 3
59
10 Chemical Thermodynamics Recipe

A common question is what conversion of a particular
reaction will be achieved at temperature T, pressure p, if
equilibrium is attained.
Write down the chemical evaluation, and look up the values at 298
K of Hf0 and either S0 or Gf0. Also look up expressions for CP of
the species involved.
Two equivalent methods. Method 1:
o Evaluate H0(298 K), G0 (298 K) and thus get K(298 K)
= exp(-G0/RT)
o Evaluate CP0, and use this to get an expression for H0 as
a function of T.
o Put this expression into the vant Hoff equation and
integrate to find the value of K(T).

Handout number 3
60
Method 2:
o Evaluate H0(298 K) and S0 (298 K)
o Evaluate CP0, and perform the integrals to get H0(T) and
S0(T)
o Hence calculate G0(T) = H0(T) T S0(T), and then get
K(T) = exp(-G0/RT).
In both cases, K can be used to predict the conversion of reactant if

equilibrium is achieved at the stated T and p.

Handout number 3
61
Part B: Reaction Kinetics

1
Introduction
Chemical thermodynamics has answered the question can a

specified chemical reaction take place? (i.e. is the reaction
thermodynamically favourable).
However, chemical thermodynamics hasnt answered the question
how fast will a specified chemical reaction occur?
o Many thermodynamically favourable reactions are
so
slow that they can be considered not to happen!

We thus need to know about reaction kinetics, as well as
thermodynamics, in order to be able to predict the behaviour of
chemical reactions.
At the fundamental level we would like to know what happens if
two (or more) molecules collide and whether this encounter leads
to the formation of new species.

Handout number 4
62
2 Rate of Reaction
Chemical engineers define rA, the rate of reaction of species A, as
the number of moles of A created per second per unit volume.
o For a batch system:
, where NA is the number of
moles of A in the vessel

o For the
volume,
special case of a batch system at
constant
this gives:
o For a continuous system:
where
is the
number of moles of A in the universe. (Note that a continuous

system at steady state has dNA/dt and dCA/dt = 0).
Handout number 4
63
o Units of rA are mol dm-3 s-1 or similar.
2.1 Rate Law Expressions

We obtain expressions for rates of reaction in terms of the
concentrations of the species present. These are termed rate laws.
General rate law expression:
o Note chemists often use [A] to denote the concentration of
reagent A.
In some cases, the rate law is a simple function:
o For example, the reaction: A + B products, may have rate
law:
o This example is 1st order with respect to A and 1st order with
respect to B. The overall order of reaction is 2.
o k is called the rate coefficient or rate constant.
o Note that the units of k change
order of the reaction.
depending on the overall
For first order it has units of time-1.
For second order it has units of conc.-1 time-1

Handout number 4
64
In other cases, the rate law may not be such a simple expression:
o For example:
o This example is 1st order with respect to A, but the order with
respect to B varies between 0 and 1 depending on the magnitude
of k2CB.
The stoichiometric coefficients i in a reaction need to be kept in
mind when considering the rates of reaction of different species:
o For example, consider the reaction: A + 2B 3C
o In this case, every mole of A reacting consumes two moles of B
and produces 3 moles of C
o Mathematically: rA = rB / 2 = + rC / 3
o In general, ri / i is a constant for a chemical reaction.
The stoichiometric coefficient is often taken into account when
defining the rate constant of simple-order reactions. For instance,
the rate constant k for the second-order reaction 2A products is
conventionally defined through
, because each of the
reaction as written removes 2 molecules of A.

Handout number 4
65
Rate law expressions cannot normally be written down by

inspection. This is partly because the overall reaction may actually
depend on a sequence of different reaction steps (the reaction
mechanism).
3 Measuring rate constants
In many cases, the change in concentration of reagents

and/or products can be followed over time
(e.g. spectroscopically by following a change in the absorbance of
a particular light frequency, or by following a change in
conductivity or some other physical parameter).
o This enables the order of reaction to be checked, and the rate
constant obtained.
Example: 1st order reaction, batch system, constant volume:
graph of ln(CA) against t will be linear in this case with

gradient k1
Handout number 4
66
Example: 2nd order reaction, batch system, constant volume:
graph of 1/CA against t will be linear in this case with

gradient k2
In some cases, the concentration of one reagent may be greatly in
excess so that it has negligible change during the reaction with
another component.
o For instance, a reaction A + 2B products with rate law
may be treated as having approximate rate law
if the concentration of B is far greater than the
concentration of A. In this special case, experimental rate data
could be analysed assuming pseudo-first-order behaviour.
Rate constants can also be obtained from just the initial value of
the rate of reaction at time t=0 if the form of the rate law is known.
Note that rate constants have units (e.g. s1 for a first-order
reaction; [concentration]1s1 for a second-order reaction).
Handout number 4
67
4 Reaction mechanisms
An overall reaction may actually depend on a sequence of different
reaction steps.
Elementary reactions are the simplest reaction steps

possible. They represent the actual molecular collisions
occurring when chemical bonds are made and/or broken.
o This means that the rate expression for an elementary reaction
can be written down by inspection (unlike the overall rate law
expression).
Example: the reaction between NO and O2 is believed to take place
according to the following reaction mechanism:
1. 2NO N2O2
- elementary reaction, rate = k1[NO]2 by
inspection
2. N2O2 2NO
- elementary reaction, rate = k2[N2O2] by
inspection
3. N2O2 + O2 2NO2
- elementary reaction, rate = k3[N2O2][O2]
by inspection
Handout number 4
68
The overall reaction is 2NO + O2 2NO2. The overall rate

expression cant be written down by simple inspection (but we will
derive it in a later section).
In some cases, the
rate-determining step
in the
reaction mechanism can be identified and this might allow the

overall form of rate law to be predicted. For instance in the
mechanism for reaction between NO and O2 above:
o If reaction 1 is the rate-determining step (and so reaction 3 is
rapid), we would anticipate the overall rate law to be rate =
k1[NO]2 (and be independent of oxygen concentration).
o On the other hand, if reaction 3 is the rate-determining step:
We anticipate overall rate law to be rate = k3[N2O2][O2]
But when reaction 3 is rate limiting, we know that
reactions 1 and 2 are rapid. This implies that 2NO N2O2
will be at thermodynamic equilibrium. Hence [N2O2] =
K[NO]2 where K is an equilibrium constant.
Hence in this case we expect overall rate = k3K[NO]2[O2]

Handout number 4
69
4.1 Comment on proving reaction mechanisms

In real life it is not possible to prove a reaction mechanism
is correct from experimentally observed rate laws all one
can do is show that a proposed reaction mechanism is
consistent with the experimental rate law.
For instance, the reaction between NO and O2 is observed
experimentally to be 2nd order with respect to NO, and 1st order
with respect to O2.
o This supports the mechanism proposed above with step 3 being
the rate-determining step.
o The evidence doesnt, however, prove that the proposed
mechanism is correct there may be another mechanism that
gives a similar overall rate law.
o More evidence, such as the detection of the N2O2 intermediate
by spectroscopic means, is required for one to be able to say the
proposed mechanism is correct.

Handout number 4
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4.2 The steady state hypothesis

The steady state hypothesis (SSH) is commonly used to predict
overall rate laws from a reaction mechanism.
This states that the concentration of any reactive intermediate
species involved may be taken as constant. i.e. they are being
removed by reaction at the same rate that they are being

formed.
For instance, in the mechanism for reaction between NO and O2,
we can treat N2O2 as a reactive intermediate and assume that it is at
steady state.
In that case:
o SSH states that
=0
o But the elementary reactions imply:

= k1[NO]2 k2[N2O2] k3[N2O2][O2]
o This gives

Handout number 4
71
o Overall rate of product formation = k3[N2O2][O2] =
o Overall rate of product formation =

(where C = k1/k2)
Note that this derivation hasnt made an assumption about what is
the rate-determining step.
o If (k3/k2)[O2] << 1, then overall rate = k3C[NO]2[O2] which
corresponds to the equation envisaged if step 3 was the ratedetermining step.
o If (k3/k2)[O2] >> 1, then overall rate = k1[NO]2 which
corresponds to the equation envisaged if step 1 was the ratedetermining step.
o If (k3/k2)[O2] ~ 1, then we need the full rate expression, as
reaction steps 1 and 3 are both influencing the overall rate.
Note that in more complicated reaction mechanisms, it may be
necessary to assume more than one intermediate species is at
steady state.

Handout number 4
72
5 Chain reactions
Some reactions take place as a chain-like process after undergoing
an initiation step that generates a source of reactive intermediate
species (e.g. free radicals).
o For example, a small number of molecules might undergo
thermal dissociation at high temperatures (their weakest bond
will break).
o UV light is a possible source of initiation at low temperatures as
it can break bonds. The rate of the initiation step will depend on
the intensity of irradiation in this case.
Example: pyrolysis (= thermal decomposition in the absence of air)
of acetaldehyde to give methane and carbon monoxide. Mechanism
(ignoring formation of side-products):
o Initiation:
CH3CHO CH3 + CHO (weakest bond
broken by temperature)
o Propagation:
CH3CHO + CH3 CH4 + CH3CO
o Propagation:
CH3CO CH3 + CO
o Termination:
CH3
+ CH3 C2H6
Handout number 4
73
o Analysis using the steady-state hypothesis for the reactive

radicals CH3 and CH3CO predicts that the rate of formation of
methane is proportional to [CH3CHO]3/2 (as observed
experimentally).
Elementary reactions in a chain mechanism are classified as:
o Initiation steps: generate reactive species
o Propagation steps: form a product while leaving the number of
reactive species unchanged
o Termination steps: form a product while reducing the number of
reactive species
o Branching steps:
these are reactions that increase the
number of reactive species (e.g. one radical reacts to form two

radicals; branching steps can lead to explosions)
o Retardation steps:
these form starting material again
while leaving the number of reactive species unchanged

o
Inhibition steps:
these remove reactive species without
forming a product (e.g. reaction of free radicals at the wall of

the vessel)
Handout number 4
74
6 Temperature dependence of rate constants

Rate constants are often found to obey the Arrhenius equation:
where A is a constant and is called the pre-exponential factor, and

Ea is termed the
activation energy
for the reaction.
Examples:
2N2O5(g) 4NO2(g)+O2;
Ea=160 kJ mol-1
Cl(g)+O3(g) CLO(g) +O2(g);
Ea=2.1 kJ mol-1
CH(g)+CH4(g) C2H4(g)+H(g);
Ea= -1.7 kJ mol-1
If rate constants are measured at more than one temperature, then
the Arrhenius parameters A and Ea may be obtained from a graph
of ln k against 1/T. (Arrhenius plot)

Handout number 4
75
Knowledge of the Arrhenius equation parameters allows us to

predict reaction rates at other temperatures.
The value of A corresponds to the rate constant predicted at infinite
temperature. For first-order reactions it is usually of the order of
1013 s1. This corresponds to the frequency of molecular
vibrations.
Bond breaking cant take place faster than this.

Handout number 4
76
What is the justification for the form of the Arrhenius equation?

Can we predict the parameters A and Ea without measuring them
directly? We shall describe briefly two models that help answer
these questions:
o kinetic theory of gases

o transition state theory
7 Kinetic theory of gases

Used for predicting rates constants of gas-phase reactions.
Consider the elementary gas-phase reaction A + B products
The number of collisions per second per unit volume between gas
molecule A and gas molecule B depends on their concentration:
ZAB = CACB.
For ideal gases may be predicted from the kinetic theory of
gases:
o this assumes that molecules in gases behave as solid
spheres moving in random directions with a distribution of
velocities.

Handout number 4
77
o result: number of collisions per second depends on the size

of the molecules, their mass, and it has a weak temperature
dependence.
However, only a certain fraction of collisions will result in
reaction:
o the molecules need
sufficient energy
to break the
bonds necessary for the reaction to take place: the

probability that they have sufficient energy is given by
exp(Ea/RT) where Ea is an activation barrier that needs to
be overcome.
o there will also be an
orientation dependence
; for
instance, the molecules may need to collide head-on or

side-on to react. The fraction of molecules that collide in
the correct orientation is .
This leads to an overall expression: rate = exp(Ea/RT) CACB
from which the Arrhenius parameters A and Ea can be identified.

Handout number 4
78
8 Transition state theory

During a chemical reaction, there is an energy
barrier that needs
to be overcome (otherwise the reaction would take place

instantaneously).
This can be represented diagrammatically in a reaction profile
diagram:
transition
Energy
state
Ea
Reagents
Products
Reaction coordinate
The reaction coordinate axis is a description of the course of the

reaction:
o e.g. for H + F2 HF + F it could be related to the HF
distance.

Handout number 4
79
The parameters A and Ea can be predicted theoretically using a

science called statistical thermodynamics. The result (not proven
here) is that:
o The parameter A includes, among other terms, the entropy
change S to get to the transition state
o Ea is the enthalpy change H to get to the transition state.
For this reason, reaction profile diagrams are often drawn
with enthalpy rather than energy on the vertical axis:
Enthalpy
Products
Reagents
Reagents
Products
Exothermic
Endothermic
reaction
reaction
Reaction coordinate
Do not confuse the transition state with a reaction intermediate:

o The transition state occurs at an energy maximum: such
species
cant be detected
though theoreticians

Handout number 4
80
infer that they exist for ~1013 s (the duration of a

molecular vibration).
o A reaction intermediate occurs at a local energy minimum;
such species exist for finite times and can be detected (e.g.
spectroscopically) or even isolated in some cases.
Energy
Intermediate
Reagents
Products
Reaction coordinate
9 Catalysts
A catalyst is a substance that increases the rate of a chemical
reaction without being consumed in the process.
Catalysts function by altering the reaction mechanism to provide a
more facile route for the reaction (e.g. one that has lower activation
energy).

Handout number 4
81
Note that catalysts cant change the thermodynamics of a chemical

reaction:
a thermodynamically unfavourable reaction will never
go, no matter what catalyst is present.

You cant get more conversion than that predicted by
thermodynamic equilibrium constants, no matter what catalyst is

present.
In
homogeneous catalysis
, the catalyst and reagents are
all in the same phase.

Example: dissolving a few drops of Br2 in aqueous H2O2
causes decomposition of hydrogen peroxide to take place in a

few minutes (rather than several weeks in the absence of Br2).
Probable mechanism:
In
H2O2 (aq) + Br2 (aq) 2Br (aq) + 2H+(aq) + O2 (g)
H2O2 (aq) + 2Br (aq) + 2H+(aq) 2H2O (l) + Br2 (aq)
Overall: 2H2O2 (aq) 2H2O (l) + O2 (g)
heterogeneous catalysis
, the catalyst and reagents are
in a different phase.
Handout number 4
82
Example: N2 + H2 do not normally react together, but in presence of a solid

metal catalyst (usually Fe) at 250C they form ammonia.
Simplified mechanism is:

N2 (g) N2 (ads) 2N (ads)
H2 (g) 2H (ads)
N (ads) + 3H (ads) NH (ads) + 2H (ads)
NH2 (ads) + H(ads) NH3 (ads) NH3 (g)
The rate of a heterogeneous catalysed reaction may be limited by
the surface area of the catalyst, or by the rate of molecular
transport between the different phases (rather than by the actual
step in which chemical bonds are made/broken).
Other species on the metal surface can influence the reaction rate:
poisons on the surface slow down the reaction
promoters on the surface enhance the reaction.

Handout number 4
83
Part A: .......................................................................................................................................1
Thermodynamics of Chemical Reactions............................................................................1
Introduction................................................................................. 1
Definitions and Assumptions...................................................... 2

2.1
Functions of two variables .....................................................................................2
2.2
Ideal Gas Law ........................................................................................................3
2.3
Internal Energy.......................................................................................................3
2.4
System and surroundings .......................................................................................4
2.5
State functions and path functions .........................................................................5
2.6
Intensive and Extensive Properties ........................................................................6
2.7
Exact and inexact differentials:............................ Error! Bookmark not defined.
2.8.......................................................................................................................................6
2.9
Thermodynamic processes................................... Error! Bookmark not defined.
The 1st law of thermodynamics................................................. 10
Heat capacities .......................................................................... 12

4.1
Estimation of CP and CV ......................................................................................14
Energy changes during a chemical reaction.............................. 16

5.1
Evaluation of enthalpies of reaction ....................................................................17
5.2
How does Hreaction vary with T?.....................................................................20
5.3
Other useful enthalpies ........................................................................................22
Entropy and the 2nd law of thermodynamics............................. 25

6.1
Variation of entropy with temperature.................................................................30
6.2
Measurements of entropies ..................................................................................31
Gibbs free energy...................................................................... 33

7.1
Gibbs energies......................................................................................................35
7.2
The master equations ...........................................................................................36
7.3
Evaluating Greaction at a specified T................................................................37
7.4
How G varies with T ............................................................................................39
Ideal Mixtures ........................................................................... 40

8.1
Mixing of ideal gases ...........................................................................................41

Handout number 4
84
8.2
Reacting mixtures ................................................ Error! Bookmark not defined.
8.3
The chemical potential.........................................................................................44
Equilibrium constants ............................................................... 46

9.1
Derivation of equilibrium constant (gases)..........................................................50
9.2
General case (solids and gases)............................................................................47
9.3
Le Chateliers principle........................................................................................52
9.4
Variation of K with temperature ..........................................................................53
9.5
Use of equilibrium constant K .............................................................................56
9.6
Some points to note..............................................................................................58
10 Chemical Thermodynamics Recipe .......................................... 59

1
Introduction............................................................................... 61
Rate of Reaction........................................................................ 62
2.1
Rate Law Expressions..........................................................................................63
Measuring rate constants........................................................... 65
Reaction mechanisms................................................................ 67
4.1
Comment on proving reaction mechanisms.........................................................69
4.2
The steady state hypothesis..................................................................................70
Chain reactions.......................................................................... 72
Temperature dependence of rate constants ............................... 74
Kinetic theory of gases.............................................................. 76
Transition state theory............................................................... 78
Catalysts.................................................................................... 80

Handout number 4

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CET 1 (convergence):

CFK, Phys Chem. I (convergence)

CFK, Phys Chem. I (convergence)

CFK, Phys Chem. I (convergence)

CFK, Phys Chem. I (convergence)

during the reaction?

by the reaction, or will only partial conversion

CFK, Phys Chem. I (convergence)

2 Definitions and Assumptions

This relationship is shown graphically on the 3D diagram below.

CFK, Phys Chem. I (convergence)

At any point on the diagram, we may define

with respect to T and p. This allows us to write the total

2.2 Ideal Gas Law

Ideal gas behaviour is based on assumption that:

between molecules are

( U ) depends only on energy states of individual

CFK, Phys Chem. I (convergence)

Therefore, internal energy is a function only of temperature. i.e.:

2.4 System and surroundings

System: what we are interested in, i.e. the species undergoing

Surroundings: what the system is interacts with, i.e. beaker,

CFK, Phys Chem. I (convergence)

It may seem strange we have to consider the

looking at questions such as: how much product is produced by the

increase in the universe as a result of the reactions.

2.5 State functions and path functions

Different paths may be followed in going from state 1 to state 2.

CFK, Phys Chem. I (convergence)

state function is a variable that depends only on the present

condition of the gas. It is independent of the route the gas followed

path function this is not the case, e.g. heating a system

(heat input = dQ) is path dependent. The quantity of heat energy

differentials, and path functions as inexact differentials

Intensive properties: independent of size of system (e.g. p, T, V,

Extensive properties: depend on size of system (e.g. V, U), and

CFK, Phys Chem. I (convergence)

2.7 Relations between partial derivatives

If the total differential of a function is constant (e.g. dV = 0) we may

CFK, Phys Chem. I (convergence)

C. Partial derivatives with the same variable held constant may be

manipulated like fractions

, where f is a function of T and p.

D. A derivative may be formed from the total differential

(ii) Confirm, for an ideal gas that:

(iii) Confirm, for an ideal gas that:

CFK, Phys Chem. I (convergence)

CFK, Phys Chem. I (convergence)

3 The 1st law of thermodynamics

closed system (= a system that has no material

entering or leaving, but energy can be added/lost).

dU = change in specific internal energy of the

work done on the system

o If the volume of the system increases by an amount dV,

Expansion Work = pdV

CFK, Phys Chem. I (convergence)

o Other work terms (e.g. electrical work to drive a current

through a circuit, or work to rotate a turbine blade) are

i.e. in this case change in internal energy is the heat

o At constant pressure we have: dU + pdV = dQ

Thus in this case dH

i.e. in this case change in enthalpy of the system is

CFK, Phys Chem. I (convergence)