Heat and Mass Transport I

Haroon Chughtai
Heat and Mass

Transport I
Thermodynamics, Diffusion, Chemical
Kinetics and Heat Transfer
Haroon Chughtai Heat and Mass Transport I 10/04/2013
Contents
1. Introduction to Thermodynamics .............................................................................................. 5
Key Concepts ....................................................................................................................................... 5
Energy ............................................................................................................................................. 5
Heat ................................................................................................................................................. 5
Systems and Surroundings .............................................................................................................. 6
Exothermic/Endothermic and Exergonic/Endergonic Processes .................................................... 6
Sign Convention .............................................................................................................................. 6
The Laws of Thermodynamics ............................................................................................................ 6
The Zeroth Law ............................................................................................................................... 6
The First Law ................................................................................................................................... 7
The Second Law .............................................................................................................................. 7
The Third Law .................................................................................................................................. 7
Chemistry Revision.............................................................................................................................. 7
States of Matter .............................................................................................................................. 7
Definitions ........................................................................................................................................... 8
2. The First Law ............................................................................................................................ 9
Internal Energy .................................................................................................................................... 9
Heat ................................................................................................................................................. 9
Work................................................................................................................................................ 9
Work of Expansion .............................................................................................................................. 9
Expansion of a Gas against Constant Pressure ............................................................................. 10
Isothermal Reversible Expansion .................................................................................................. 10
Irreversible Expansion ................................................................................................................... 10
Digression.......................................................................................................................................... 11
State and Path Functions .............................................................................................................. 11
Exact and Inexact Differentials ..................................................................................................... 11
3. Heat Capacity, Enthalpy and Thermochemistry ....................................................................... 12
Heat Capacity .................................................................................................................................... 12
Molar Heat Capacity ..................................................................................................................... 12
Isochoric Heat Capacity, .......................................................................................................... 12
Isobaric Heat Capacity, ........................................................................................................... 12
Enthalpy ............................................................................................................................................ 13
Thermochemistry .............................................................................................................................. 13
Hess’s Law ......................................................................................................................................... 13
Temperature Dependence of ................................................................................................. 14
1
4. Entropy and the Second Law................................................................................................... 15

Spontaneous Processes .................................................................................................................... 15
Examples ....................................................................................................................................... 15
The Second Law ................................................................................................................................ 15
Statements of the Second Law ..................................................................................................... 16
Entropy.............................................................................................................................................. 16
Calculating Entropy ....................................................................................................................... 16
Entropy as a State Function .......................................................................................................... 17
Entropy of Expansion of a Gas ...................................................................................................... 17
Surroundings and Heat Flow ......................................................................................................... 17
5. Free Energy ............................................................................................................................ 18
Introduction ...................................................................................................................................... 18
Gibbs Free Energy ......................................................................................................................... 18
Helmholtz Free Energy .................................................................................................................. 18
Gibbs Free Energies of Formation..................................................................................................... 18
Chemical Potential and Equilibrium .................................................................................................. 19
Linking G to Chemical Composition .............................................................................................. 19
Chemical Potential. .................................................................................................................. 19
Equilibrium between gaseous reactants....................................................................................... 19
Dilute Solutions ............................................................................................................................. 20
Temperature Dependence of G ........................................................................................................ 21
Temperature Dependence of Equilibrium Constants: Van’t Hoff Isochore ...................................... 22
Le Chatelier’s Principle .................................................................................................................. 22
Electrical Potential ........................................................................................................................... 22
Electrode Potentials and Electrochemical Cells ............................................................................ 22
Membrane Potential ..................................................................................................................... 23
6. Diffusion in Liquids ................................................................................................................. 24
Flux .................................................................................................................................................... 24
Fick’s First Law .................................................................................................................................. 24
Fick’s Second Law.............................................................................................................................. 24
Steady State Diffusion ................................................................................................................... 24
Example: Diffusion through a slab or flat membrane ................................................................... 24
What Drives Diffusion? ..................................................................................................................... 25
Examples ....................................................................................................................................... 25
Average Distance Diffused in Time, t ................................................................................................ 26
7. Ions in Solution ...................................................................................................................... 27
2
Water ................................................................................................................................................ 27
Coulomb’s Law .................................................................................................................................. 27
Dissolving Ions................................................................................................................................... 28
The Bjerrum Length, ................................................................................................................... 28
Solubilities of Ionic Solids in Water ............................................................................................... 29
Organic Solubility .......................................................................................................................... 29
Quantitative Approaches to Ionic Solubility ..................................................................................... 29
Calculating solubility from (and vice-versa) ......................................................................... 30
8. Ionisation and Acidity ............................................................................................................. 31
Strengths of Acids ............................................................................................................................. 31
Henderson-Hasselbalch Equation ................................................................................................. 31
Strengths of Bases ......................................................................................................................... 31
Buffers ............................................................................................................................................... 31
Example ............................................................................................................................................. 32
9. Gases in Solution .................................................................................................................... 33
Dalton’s Law ...................................................................................................................................... 33
Henry’s Law ....................................................................................................................................... 33
Methods of Expressing Gas Solubility ........................................................................................... 33
Henry’s Law Constant, KH .............................................................................................................. 34
Vapour Pressure of Water ............................................................................................................ 34
Worked Example ........................................................................................................................... 34
Temperature Effects ..................................................................................................................... 35
10. Chemical Kinetics ................................................................................................................. 36
Reaction Rate .................................................................................................................................... 36
Empirical Rate Equations .................................................................................................................. 36
Order of Reaction.............................................................................................................................. 36
Zeroth Order ................................................................................................................................. 36
First Order ..................................................................................................................................... 36
Second Order ................................................................................................................................ 36
Third Order and Higher ................................................................................................................. 37
Reactions with No Order: Enzymes .................................................................................................. 37
Determination of the Rate Law......................................................................................................... 37
The Ostwald Isolation Method ..................................................................................................... 37
The Method of Initial Rates .......................................................................................................... 37
Integrated Rate Laws .................................................................................................................... 37
Effect of Temperature on Reaction Rate .......................................................................................... 39
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The Arrhenius Equation ................................................................................................................ 39

Collision Theory – Incorrect Model ............................................................................................... 39
Transition State Theory ................................................................................................................. 39
Enzyme Catalysed Reactions ............................................................................................................. 41
Example: Decomposition of Hydrogen Peroxide .......................................................................... 41
Michaelis-Menten Kinetics............................................................................................................ 42
Inhibition of Enzyme Reactions..................................................................................................... 43
Chemical Kinetics Summary .............................................................................................................. 44
11. Steady State Heat Transfer ................................................................................................... 45
Conduction: Fourier’s Law ................................................................................................................ 45
Example in 1D ............................................................................................................................... 45
Conduction through multi-layered wall: The resistance network analogy................................... 45
Example: Human Tissue ................................................................................................................ 46
Multidimensional Conduction: The General Conduction Equation .................................................. 46
General conduction equation simplification ................................................................................ 47
Solving the General Conduction Equation .................................................................................... 47
Natural Convection: Newton’s Law of Cooling ................................................................................. 48
Combined conduction and natural convection example .............................................................. 48
Radiation: Stefan-Boltzmann Law ..................................................................................................... 49
Properties and Definitions ............................................................................................................ 49
Black Body: Ideal Receiver, Ideal Emitter ..................................................................................... 49
The Stefan-Boltzmann law ............................................................................................................ 50
Grey Bodies ................................................................................................................................... 50
Further Examples .......................................................................................................................... 51
Putting it all together ........................................................................................................................ 51
4
1. Introduction to Thermodynamics
 Thermodynamics underpins all chemical processes and reactions
 Thermodynamics is universal and never wrong
o If a process appears to break it, our analysis is wrong or incomplete
 Essentially concerned with:
o Conservation of energy
o Transfer of energy (through work or heat)
 It predicts:
o Spontaneous direction of chemical processes or reactions
o The equilibrium states of chemical systems
 It doesn’t deal with rates of processes
o This is the subject of chemical kinetics
 Arose in 19th century due to need to improve steam engines
o Results applied to all chemical and physical systems
Key Concepts
Energy
 Energy comes as heat ( ) and work ( )
Heat
 The transfer of energy due to a difference in temperature between the
system and its surroundings
 Transfer due to chaotic, disorganised motion (i.e. thermal motion) of particles
o E.g. Two metal blocks at different temperatures in thermal contact
Work
 A process which could be used directly to move an object a certain distance
against an opposing force
 Transfer due to organised motion of particles
o E.g. atoms in a piston all move in the same direction
 ∫
o Where
 If force is constant, and in opposite direction to direction of motion of object, this

simplifies to:
o
 Many different types
of work 
5
Systems and Surroundings

 Thermodynamics divides the universe into two parts:
o System: region of chemical interest
 A reaction vessel, characterised by
properties such as , etc.
o Surroundings: The rest of the universe, the region
outside the system
 Separated by a boundary
 Concerned with exchange of energy and matter between
the system and its surroundings
 Systems are classified according to the constraints on
energy and matter exchange:
o Open system: Both energy and matter can be
freely exchanged
 The Earth could be considered such a system
to a degree
o Isolated system: Neither energy nor matter can be
exchanged
 A perfect thermos is an example if it does not
expand/contract and is thermally isolated
o Closed systems: Only energy can be exchanged
 Adiabatic system: Only work exchanged
(thermally isolated)
 Diathermic system: Only heat exchanged
 It matters how the energy is exchanged as this affects the
maths we can use
Exothermic/Endothermic and Exergonic/Endergonic Processes
 Exothermic : The system gives out heat
 Endothermic: The system takes in heat
 Exergonic: The system gives out energy

 Endergonic: The system takes in energy
Sign Convention
 As biomedical engineers we are concerned with the system
o Energy taken in by the system is positive
o Energy given out is negative
 This is easy to remember if you consider that giving a (living) system energy is
positive but energy taken away from it is negative
The Laws of Thermodynamics

 There are four Laws of Thermodynamics
The Zeroth Law
 There is a unique scale of temperature
o This is known as absolute temperature and
measured in Kelvin
o At 0K, energy of a particle is 0
o Also if body A is in thermal equilibrium with body
B, and B with C, then A is also in thermal
equilibrium with C
6
The First Law

 The energy of an isolated system is constant
o Energy cannot be created nor destroyed, only transferred between
systems, or between a system and its surroundings
The Second Law
 When two systems are brought into thermal contact, heat
flows spontaneously from the one at the higher
temperature to the one at the lower temperature, not the
other way around
o This is concerned with spontaneous directions of
processes, determined by changes in the entropy, .
 Also expressed as:
o Heat cannot be completely converted to work for a
cyclic process, but work can spontaneously be
completely converted into heat
o Spontaneous exchanges are always accompanied by a conversion of
energy into a more disordered form
o The entropy of an isolated system increases during any spontaneous
change or process.
The Third Law
 All perfect materials have the same entropy at absolute zero. For
. It is impossible to cool any system to
1. You can’t win, you can only break even
2. You can only break even when it’s very cold
3. It never gets that cold
Chemistry Revision
States of Matter
State Behaviour Model
Gas  Fills the container it  Widely separated particles in
occupies continuous rapid disordered
motion. (avg. in air)
 Each particle travels several
diameters before colliding with
another particle.
 The particles only interact weakly
Liquid  A fluid that  Particles in contact but able to
possesses a well- move.
defined surface.  Particles can only travel a fraction
 In a gravitational of a diameter before a collision
field it fills the lower occurs.
part of its container.
Solid  Retains its shape.  Particles are in contact & unable
to move past each other.
 Particles oscillate around an
average location but are
essentially trapped
 Frequently lie in more or less
ordered arrays
7
Definitions
 Physical state: The condition of a sample of stuff in terms of physical form (gas,
liquid, solid), V, T, p, amount, n.
 Force: A body travels in a straight line at constant speed unless acted on by a
force.
o .
o Measured in newton, N.
 Work: Force  distance
o ∫
 Pressure: Force per
unit area
o
o Can arise from
numerous
collisions of
gas molecules
o SI unit is the
 Also measured in atmospheres (atm), mmHg, bar and
 Temperature, T: Property that determines direction of energy flow
o
 Volume, V: the space occupied by a system
o Is an extensive property and a state function
 Energy, J: Capacity to do work
o
o
o
 Amount of stuff: Mass (kg) is independent of identity.
o However if we study ensembles of particles, mole is the appropriate unit.
 1 mol is the number of particles in exactly 12 g of 12C.

o
 Molar mass, : Mass per mole of substance,
o e.g.
o
 RMM: Relative molecular mass is the atomic or molecular mass relative to 12C.
 Concentration: The amount of solute per unit volume of solution
o
o Common units of concentration:
 : Litre is not SI. Decimetre, dm is more explicitly related to
m3, the SI unit. Also known as molarity.
 Molal: moles per kg of solution
 %(w/w): weight of solute per weight of solution expressed as a
percentage
 ppm: parts per million: weight of solute.
 Extensive property: depends on amount, e.g. mass, volume.
 Intensive property: independent of amount e.g. T, p.
o Some intensive properties are the ratios of two extensive properties e.g.
density, concentration.
8
2. The First Law
Internal Energy
 The internal energy, U of a system is the total energy it
contains as a result of its physical state
o That is under specified conditions of T, p, V, etc…
 The First Law states that the internal energy of a system is
constant unless it is changed by work, w or by heat transfer, q
o
 does not depend on how that state was reached: it is path independent
o is said to be a state function
 is also an extensive property of the system
o Doubling the mass, doubles
 The intensive version of this is:
 In microscopic terms, is equal to the total sum of the energy levels of the
atoms or molecules making up the system, weighted by their probabilities
of being occupied
Heat
 “The transfer of energy due to a difference in temperature between the
system and its surroundings”
o If is positive and heat flows into the system,
raising its internal energy
o If is negative and heat flows out of the system,
lowering its internal energy
 Example: A sealed flask of nitrogen gas placed in a hot oven
o Heat will flow into the flask ( ), raising the temperature and internal
energy of the gas (by increasing the populations of the higher energy
levels of molecules)
Work
 “A process which could be used directly to move an object a certain distance
against an opposing force”
 Generally defined by the integral of the vector dot product of the force F and the
small incremental displacement ds:
o ∫
 If force is constant and in opposite direction to direction of motion, this
simplifies to, where is the distance the object has moved:
o
Work of Expansion
 Consider the work of expansion of a gas
 The work done by the system against the surroundings in
moving a piston of area by distance against an
opposing force :
o
 The system will expand if
 For a positive (expansion), work is
negative as the internal energy of the
system decreases by carrying out work
on the surroundings
9
 The system will compress is

 For a negative (compression), work is positive as the
internal energy of the system increases.
 Note that it is the external pressure which determines the amount of
work done, not the system pressure,
Expansion of a Gas against Constant Pressure
 The work of expansion of a gas against a constant external pressure is:
 ∫
o ∫
o ( )
o
 The work is negative for positive (i.e. work done by
the system)
 The magnitude of the work may be illustrated by the use of
an indicator diagram Plot of versus
o Note that this doesn’t give sign
Isothermal Reversible Expansion
 For the expansion to be carried out reversibly, must be
adjusted to be equal to at each infinitesimal step in the
expansion
o This keeps the system in equilibrium at all times
 Thus as :
o ∫ ∫
 The pressure, of the system is given by the
equation of state of the gas
o This is for an ideal gas
o This integral can be evaluated directly if T
is constant (i.e. isothermal)
 Thus for an ideal gas:
o ∫
Irreversible Expansion
 If expansion is carried out irreversibly, by suddenly lowering from to
, the expansion occurs against a constant external pressure,
o The work of expansion is therefore:

 Result applies when the system is either adiabatic or isothermal
o The work performed in an irreversible expansion is smaller in
magnitude than the work of a reversible expansion
o | | | |
 “A system operating between specified initial and final states does the
maximum work when the process is carried out reversibly”
10
Digression
State and Path Functions
 Clearly work is not a state function as different work was done between the
same states and in the reversible and irreversible states.
o Heat transfer is also different and so not a state function
 Work and heat are referred to as path functions
o Their values depend on the path taken between the initial and final
states
Exact and Inexact Differentials

 The state of a perfect gas is defined by specifying and .
o As specifying any two of the variables fixes the third
o Thus is known as an equation of state
 is different from and as it only depends on the state of the system
o Thus U has a definite value for say a particular and
 If a state function is integrated, it has a definite value:
o ∫
o This is independent of the path taken between A and B
o is an exact differential
 can be written as an exact differential:
o If internal energy is a function of and

 ( ) ( )
o The order of differentiation does not affect the result
 and cannot be expressed this way as they are inexact differentials,
which means that and are path functions
11
3. Heat Capacity, Enthalpy and Thermochemistry
Heat Capacity
Molar Heat Capacity
 Molar heat capacity, is the amount of energy required to raise 1 mol of a
substance by 1K
o
 Strictly the heat capacity is the increment in heat required to increase
the temperature of a system by an amount
o
o This is an extensive property so often divided by to give molar heat
capacity
Isochoric Heat Capacity,
 This is where the volume of the system is constant (in bioreactors, etc.)
o Thus no work can occur as
 So assuming no other work, from First Law
o
o ( )
Isobaric Heat Capacity,

 This is where the pressure of the system is constant (in cells, etc.)
 If heat is supplied at a constant sample pressure, the sample will expand
o Work will be done against the external pressure
 This means that not all the heat will be used to raise the temperature
o A greater heat flow, will be required to raise the temperature by the
same amount as in the isochoric case
o So usually
 So assuming no other work, from First Law
o //work done by system so –ve sign
o
o ( )
Temperature Dependence of
 varies with the temperature
12
 For some systems (e.g. monoatomic gases), is temperature independent

o However for most systems the heat capacity varies with temperature
o At phase transitions,
 As heat flow does not change with temperature until latent
heat of the transition has been supplied
 Within the gas phase it is expressed as a power series:
o (Antoine equation)
Enthalpy
 If there is no work other than work;
o
o
 Thus:
o
 And so:
o ( ) ( )
 Enthalpy, is a state function and so useful in thermochemistry
o The change in enthalpy, is equal to the heat flow at constant
pressure. This often applies
 For nearly incompressible solids and liquids, so
 For an ideal gas with ,
Thermochemistry
 Consider a reaction
o
 If the initial enthalpy is and the final enthalpy is the enthalpy change
upon reaction is:
o
 If is negative then heat is released and
the reaction is exothermic
 If is positive then heat is absorbed and
the reaction is endothermic
Hess’s Law
 For chemical reactions we denote the enthalpy change as known as the
reaction enthalpy
o At standard conditions ( /298 K, 1 bar/ Pa, standard states)
we refer to the standard reaction enthalpy
 As enthalpy is a state function, the total enthalpy change for a reaction is
independent of the reaction path
 So for the reaction:
o [ ]
 Where is standard enthalpy of formation of a species
 The small letters denote the number of moles involved
 In general:
o ∑ ∑
 By convention:
o is defined as zero for all elements in their standard states
 Real gases are taken to behave ideally in their standard states
o Note that has by convention
13
Temperature Dependence of
 As ( ) , it follows that:
o
 is the change in heat capacity between the two states
 Integrating from to gives:
o ∫ ∫
o ∫
 A useful form of this is:
o ̅
 Where ̅ is the mean heat capacity over the temperature
range
 If heat capacity is independent of temperature
o ̅
14
4. Entropy and the Second Law
Spontaneous Processes
 The First Law is about the conservation of energy, but can a chemical or physical
process take place spontaneously?
o The direction is not solely determined by the minimisation of the energy
Examples
 In each of these examples the spontaneous direction is obvious
o It is inconceivable that the reverse would occur without some work done
Isothermal Expansion of an Ideal Gas
 When the tap is opened, gas will flow from A to B until pressures are equal
o and for this process as ( ) and ( )
o Heat flows in from the
surroundings because the gas
in flask A performs work on
the gas in flask B as the
pressure builds up from zero
to
Thermal equilibrium
 Two identical blocks of metal, one at and
the other at a lower temperature, are
brought into thermal contact and isolated
o as isolated system
o Heat flow from A to B until blocks at
equal temperature
Endothermic solution of a salt
 If is added to water it will dissolve
o Endothermic process (
o Solution cools down as heat absorbed
Chemical equilibrium
 Consider:
o
 Spontaneous partial dissociation will occur despite
o A highly endothermic event
The Second Law

 Clearly reactions can occur spontaneously even if they are disfavoured in
terms of the enthalpy changes
o In each case the spontaneous reaction moves towards a more
disordered or more uniform state
o The systems have lost some capacity for carrying out work
15
Statements of the Second Law

 When two systems are brought into thermal contact, heat flows spontaneously
from the one at the higher temperature to the one at the lower
temperature.
 Heat cannot be completely
converted to into work for any cyclic
process but work can be completely
converted to heat.
 Spontaneous changes are always
accompanied by conversion of
energy into a more disordered form.
 The entropy, S, of an isolated system increases during any spontaneous
change or process.
Entropy
 In each case of a spontaneous process, the total entropy of the system plus its
surroundings has increased:
o Note: From here on it is
 This can be expressed in terms of the small, incremental changes presumed S denotes
in entropy occurring during the process: entropy of the system
o | spontaneous, irreversible
o | equilibrium , reversible
 For an isolated system, any spontaneous change will tend to produce states of
higher entropy, until the entropy is at its maximum.
o The system is then at equilibrium
 The lost capacity to do work must be to do with since
o Work = internal energy change – ”unavailable energy”
o
 For a reversible change, the work done by the system is a maximum.
o dw for a reversible change is more negative than for the equivalent
irreversible spontaneous change.
 dU must be the same regardless of how the change is carried out.
 Since dwrev < dwirr this implies dqrev > dqirr .
o During a reversible change, the system absorbs the maximum heat
from its surroundings and does the maximum work on its surroundings.
o Observable spontaneous processes absorb less heat and do less
work.
Calculating Entropy
 Entropy is a state function defined for a reversible process at T where q heat
is absorbed as:
o ∫
o Going from state A to state B, will always be the same
 However for a reversible change when the system is at equilibrium
o
o This is a general definition of equilibrium.
o For an isolated system, , so S is a constant
 For observable changes because
16
Entropy as a State Function

 From the First Law: (presuming system only does pV work)
 For one mole of an ideal gas: and
o
 Integration yields:
o
 Thus is an exact differential and is a state function for an ideal gas
o This turns out to be generally true
Entropy of Expansion of a Gas
 Consider the isothermal expansion of a perfect gas:
o is independent of volume, so and
o Heat gained from surroundings is equal to work done by system
 For reversible expansion:
o ( )
o ( )
 This equation only consists of state functions so this is also true for
irreversible changes.
o Heat lost by the surroundings = heat gained by the gas, so .
o For irreversible expansion, the entropy is unchanged for the system,
but different for the surroundings
Surroundings and Heat Flow
 As previously stated for all spontaneous processes:
o
o | spontaneous, irreversible
o | equilibrium , reversible
 The connection with heat flow is:
o (Clausius inequality)
o for reversible processes
 So ∫
 is difficult to assess, but
o So
o This is the criterion for a spontaneous reaction in terms of the system
o means the system is at equilibrium
17
5. Free Energy
Introduction
 The Clausius inequality ( can be rearranged to
o Since ;

Gibbs Free Energy
 Thus at constant pressure (assuming no non- work)
o
o
 So we define Gibbs free energy as:
o

o Non-spontaneous
o , Equilibrium
o , Spontaneous
Helmholtz Free Energy
 Thus at constant volume ( , assuming no work)
o
 So we define Helmholtz free energy as:
o

o Non-spontaneous
o , Equilibrium
o , Spontaneous
Gibbs Free Energies of Formation

 is the change in Gibbs free energy when 1 mol of substance is formed at 1
atmosphere and 298 K from its elements in their standard states.
o State function so can be calculated from formation values
(cf. Hess’s Law)
o ∑ ∑
 Free energies of formation of the chemical elements in their usual states
are zero.
 As bioengineers we deal with constant pressure, constant temperature
systems
o At constant pressure:
 is the additional non- work done by the system such as
electrical or new phase formation
o At equilibrium:
 and
 So


 Thus Gibbs free energy, is the max amount of reversible
(non- ) work that the system can do at constant pressure
and temperature
18
Chemical Potential and Equilibrium

 Also we know and
o So
o So (taking total differentials)
 If a system does only work:
o
o So
 Thus
o This allows us to examine the effects of pressure and temperature on G
and therefore composition through the equilibrium constant
Linking G to Chemical Composition
 At constant temperature,
o
o ( )
 For n moles of a perfect gas,
o
o So changing pressure from to :
 ∫
 Free energy of a gas is usually related to the standard free energy G which is
the free energy of one mole at one standard atmosphere pressure (not SI!).
o ( ) Where is 1 atm
o Often written as :
Chemical Potential.
 The chemical potential of component is defined as:
o ( )
o Pressure, temperature and moles of other species are held constant

 So if the number of moles of different components ( ) vary:
o ( ) ( )
 So ∑
 Thus:
o For a system at constant T, p, the chemical potential of each
component must be equal in all parts of the system for equilibrium.
 For one mole of gas: and for a pure substance, the chemical
potential is simply the molar free energy, so for some gas i:
o
o As a mixture of perfect gases behave independently of each other
Equilibrium between gaseous reactants
 For the reaction ;
o If moles of A are converted to moles of B at constant T and p
o
o Where is negative and is positive
 The extent of reaction, is 0 for pure reactants and 1 for pure products
o
o So
19
 Thus the reaction will proceed to equilibrium where G is minimum:

o ( )
o Thus
 Presuming A and B follow perfect gas law:
o ( ) ( )
o the free energy if one mole of reaction takes place
with both the product and the reactant in the standard state at 1 atm
 So at equilibrium ( )
 The ration is the equilibrium constant,

o This relates the free energy to the position of the chemical equilibrium
o More generally
o So
 This allows us to quantify the effects of and on equilibrium constant and
thus on the composition
Dilute Solutions
 We can treat all dilute equations as if they behave as gases

o Where thermodynamic activity, = is the effective concentration
 For ionic solutions:
o is the concentration in the standard state
o is the ion activity coefficient
 is a function of ionic strength, and can be calculated from
Debye-Hückel theory
 Essentially a fudge factor to allow us to pretend that most
particles interact like gases
 This will be a better approximation, the more dilute a
solution is
 Activity is particularly important in ionic solutions in allowing the use of
thermodynamic concepts in a complex situation:
o three interactions exist; ion-ion, ion-solvent and solvent-solvent.
o The use of ion activity ai allows thermodynamics of ionic solutions to be
expressed in terms of a measurable quantity: concentration
 Ionic strength, can be calculated by:
o ∑
 where is the concentration and is the formal charge on ion i
o Example: 0.1M
 ( )
 Thus mean can be approximated as such for dilute (sub mM) concentrations :
o √
o This WILL give ERRORS as it is an approximation
20
Debye-Hückel theory
 The Debye-Hückel theory allows estimation of the average activity coefficient
from physical constants and the ionic strength, for dilute solutions
o e is the charge on an electron,
o  is the permittivity of free space
o 0 is the relative permittivity
o k is Boltzmann’s constant
o a0 is the distance of closest approach,
o N is Avogadro’s number
 The characteristic length of the electric field
is given by the Debye length, 1/ :
Temperature Dependence of G
 Remember:
o
o
 But (First Law) and so (reversible change)
o
 So at constant T:
o ( )
 So at constant p:
o ( )
o As :
 ( )
 ( )
o Divide through by //the tricky bit to see
 ( )
o But from the product rule of differentiation:
( )
 ( ) ( )
( )
o So ( )
 Thus the Gibbs-Helmholtz Equation:

( )
o ( )
21
Temperature Dependence of Equilibrium Constants: Van’t Hoff Isochore

 Given the Gibbs-Helmholtz Equation:
o We can differentiate to the Van’t Hoff Isochore
( )
o ( ) ( )
 Assuming is independent of T, and integrate:

o ( )
 Allows us to calculate effect of temperature on any equilibrium constant
and constantly on composition
Le Chatelier’s Principle
 “Perturbation of a system at equilibrium will cause the equilibrium position
to change is such a way as to remove the perturbation”
o If a reaction is exothermic ( , lowering the heat will promote the
reaction
o If the reaction leads to an increase in volume, application of pressure will
favour the reactants
 Thermodynamic relationships put this quantitatively
o ( )
o ( )
Electrical Potential
 In a non-ideal solution, the change in free energy of a system when one
mole of uncharged species is added to it is given by:
o
 If the added solution is ionic, this equation no longer works as we need to take
account of the electrical potential generated by the charge on the ions
already present.
o Adding one mole of further charges, magnitude will cause an extra
change in free energy of . So:
o ̅
 ̅


 =
 New equilibrium condition
o Electrochemical potential is the same everywhere in the system for
all ions
Electrode Potentials and Electrochemical Cells
 Electrode reactions:
o

o

o Overall:


 Electrochemistry allows isolation of oxidation and reduction on electrodes
22
 Consider:
o When equilibrium is established the electrochemical potentials must
be the same on both sides of the equation
o ̅ ̅
 The electrochemical potential for each phase is given by:
o ̅
 Where is activity
o Substitution gives:

 Since copper metal is not charged, is zero
 ( ) ( )
 This is known as the Nernst Equation
 For the general electron transfer function:
o ( )
o As ( )
 ( )
 The reduction of one mole of to requires the passage of Faradays
of charge.
 The passage of coulombs of charge through a p.d. of volts gives
joules of electrical work
o
o
Membrane Potential
 Thermodynamic equilibrium exists for
o for each species is equal
o For charged species, electrical potential must be included in the
equilibrium condition
 ( )
 Electrochemical potential, ̅
 Two ionic solutions phase and phase separated by a selective membrane
o Electrochemical potential for the target species, must be equal on both
sides of membrane:
o
o
 is the membrane potential, is the gas constant, z is the charge, T is the
absolute temperature, F is Faraday’s constant and are the ion activities
in the different compartments
23
6. Diffusion in Liquids
Flux
 Consider a slab of fluid
o long
o
o Volume
o particles per unit volume
o Total number of particles:
 Flux is number of particles per area
per unit time =
 If flow velocity is then flux =
 Molecules diffuse, transporting heat and matter
o Flow of particles is described by their flux, J
o J, amount of material per unit area, per unit time
Fick’s First Law

 (in one dimension)
o Number of particles passing per unit time is proportional to the
change in concentration with position
 (in three dimensions)
 is the diffusion coefficient
o for solutes in aqueous solution at room temp
o for gases (can move many diameters without
collisions)
Fick’s Second Law

 The “diffusion equation” deals with the rate of change of concentration with time
 [ ( )] ( )
o Applies only if D does not vary with x
o Only applies in one dimension
Steady State Diffusion
 We (in this course) deal with steady state diffusion
o This means that the concentration gradient is fixed at any point
o
 So ( ) and thus ( ) (as D is a constant)
Example: Diffusion through a slab or flat membrane

 Higher solubility in the
membrane (usually lipid in cells)

o Partition coefficient
o Essentially an
equilibrium constant
 Consider the steady state flux,
and are constant
24
o ( ) Integrate with x to get:

o ( ) where is a constant. Integrate again:
o
 Concentration gradient is linear and varies with position alone
 Time independent therefore steady state
 Substituting for the concentration at gives
o At , so by substitution:
o
o
 To determine flux, , differentiate w.r.t. x and substitute in Fick’s first law
o
o
 Permeability is defined as
What Drives Diffusion?
 Consider the difference in free energy over distance where the
concentration changes from c to (c+dc) and calculate the difference between
molar Gibbs energy at c and that at (c+dc):
o Note we are using concentration, as a measure of activity,
 ( ) ( )
o As is very small: ( )

 Therefore work done by the system, -w to move one molecule from to is:
o
 and so driving force is:
o
 At constant velocity, , where is the frictional coefficient
o Limiting velocity is obtained when frictional force equals driving
force:




o Thus by comparison to Fick’s first law:

Examples
 For a sphere, giving the Stokes-Einstein equation:
o (Thermal energy driving Brownian motion vs. the viscous drag)
o is the viscosity coefficient, for water at
 More complex expressions for other shapes
o Disc moving at random:
o Ellipsoid moving at random:
( )
25
Average Distance Diffused in Time, t

 IN ONE DIMENSION!
 For small , concentration gradient
is linear
o Let be the average distance
diffused in time
 If is the flux from left to right across
the area at x=0,
o Half the molecules will cross in
time t

o From right to left;
( )

 Net flux, given by
( )
o
o
 Thus by comparison to Fick’s first law:
o
o Vitally important length scale in sensing
o Defines resolution, tells you if the molecules can even get there
26
7. Ions in Solution
Water
 Water has specific properties that
make it biologically and
chemically important
o High relative permittivity
o High dipole moment
o Good solvent for ions
 Water molecules orientate around ions to form hydrated species
 Acid-base Behaviour
o
o Also
o
 Redox Properties
o Oxidation leads to
 At +ve electrode:
o Reduction leads to
 At –ve electrode:
Coulomb’s Law
 Charge interactions are governed by Coulomb’s Law
o
 is energy of interaction
 is the distance
 , are the magnitude of the charges
 is permittivity of free space,
 Attraction between and
o Charge on proton, e is or
o
o for a pair
 However this attraction is at a long range

o Hydrogen bonds are

typically
so thermodynamically
stable
 By considering the pairwise
interactions of one ion with
every other ion, we can
obtain a more realistic
number
o Scaling factor is the
Madelung constant
for hard spheres in a cubic lattice
o Actual energy of interaction is now
27
 Electrostatic attractions are strong and long-range

o The electrostatic repulsion between two protons is 1036 stronger than the
gravitational attraction
Dissolving Ions
 Ions can dissolve as some media are
polarisable
o Fixed charges (of ions) cause
orientation of the permanent
dipoles, shielding the charges and
weakening the interaction.
o Media that shield interactions
strongly have high relative
permittivity (e.g. water)
o (Dipoles can be permanent, but also induced)
 Therefore charge interactions are weaker in media (as opposed to free space)
o
 Where is relative permittivity of the media (formerly dielectric
constant)
 Relative permittivities of various liquids at 25
C
 Liquid 
 Heptane  1.916
 Methanol  33
 Formic Acid  58
 Water  78.84
 Formamide  109
 Whole blood  8.25
The Bjerrum Length,

 The Bjerrum Length, is the charge separation at which the coulomb
energy between the ions is equal to the thermal energy,
o Sub for r and for
 In a vacuum at
o
 In water at
o
o This value is much smaller than in a vacuum
 This little more than twice the observed lattice separation, 2.81  10-10 m
 Thus salts dissolve because the ionic bonds are weak in water
28
Solubilities of Ionic Solids in Water

 Some qualitative rules of thumb for solubilities in water
o (able to achieve a solution with concentration of > 100 mol m-3)
o MEMORISE ALL THE SOLUBIILTES!
i. All Group 1A and NH4+ salts are soluble in water.
ii. All nitrate (NO3-) salts are soluble in water.
iii. Most chloride, bromide and iodide salts are soluble
o Except Ag+, Hg22+.
iv. Most sulfates are soluble
o Except Ba2+, Pb2+, Hg2+, Bi3+, Sn2+.
o CaSO4 is fairly soluble.
v. Most carbonates, oxides, hydroxides, phosphates, sulfides are insoluble,
o Subject to Rule (i).
o Ca(OH)2 and Ba(OH)2 are fairly soluble.
Organic Solubility
 Ions increase solubilities
o May be permanent (e.g. quaternary amines )
o Or ionisable groups (e.g. amines)
 →
 →
 →
 (Note left hand side volatile and RHS water soluble)
 Decrease in pH causes increase in water solubility
 Note that balance of hydrophilic and hydrophobic groups are important in drug
design so that compounds dissolve in the correct places
 Other examples: Hydrogen bonding generally increases water solubility
o Carboxylic acids:
o Primary and secondary amines: and
o Alcohols:
 Note that solubility decreases as alkyl chain length increases
o Sulfates:
o Sulfonate:
Quantitative Approaches to Ionic Solubility

 Solubility, : The number of that dissolves to form a saturated
solution at a given temperature
 Consider the equilibrium of the archetypal salt dissolving in :
o
 Equilibrium constant governing this process is the ion solubility product,
o
o The activity of the pure solid phase is omitted
 This is as we are considering the saturated solution so adding
more reactant will not increase solubility
o Activities may be approximated by ionic concentrations for
sparingly soluble salts (milliM concentrations)
 Remember that this is an approximation and can be way out
o Concentration units are non-SI
29
Calculating solubility from (and vice-versa)

 Calculate the solubility of given
o
o at saturation for a given temp
o
o
 Calculate the solubility of given
o
o
o For moles of reactant:
o
o √
 values are widely available
o These depend on the solvent and temperature
Limitations
 The concept of is a poor predictor of solubility in several cases
o This is in addition to the limitation that stems from concentration only
being a good measure of activity for sub milli-molar concentrations
Weak Electrolytes
 will underestimate the solubility of such compounds
 Strong electrolytes
o These completely ionise in water
o
 Weak electrolytes
o Incompletely ionise in water when dissolved
o
o The extra species is not accounted for by
Common Ion Effect

 Dissolution of a slightly soluble salt is inhibited if it dissolves into a
solution containing one of its component ions
 Example: Solubility of in 0.1M
o
o S S S+0.1 (This is due to the
o
o
Anion from Weak Acid: pH Effect
 For example the dissolution of

o reacts with and is removed so more dissociates to restore
Ions Complexed
 The same effect as above occurs when an ion is complexed with a ligand and so
effectively removed from the equilibrium
30
8. Ionisation and Acidity

 Bronsted-Lowry (def. used in biological systems) :
o Acids are proton donors
o Bases are proton acceptors
 Lewis:
o Acids are electron pair acceptors
o Bases are electron pair donors
 Strong acids readily donate protons and accept electron pairs
 The acidity of a solution is measured in pH units:
o
 In the physiological range it is reasonable to use instead
of activity. However this does introduce errors
o
 Clearly then, in reverse;
o
Strengths of Acids
 Strengths of acids are expressed in terms of their acid dissociation
equilibrium constants,
o
o where HA is the acid and is the conjugate base
o
 Strong acids have small values
o pH<4ish
 depends on temperature and solvent
 Acid strength is the ability to donate protons
Henderson-Hasselbalch Equation
 The previous equation can be rearranged to a more useful form:
o ( )
 When there are equal concentrations of the acid and base forms
o So if we know the of a drug we can predict its charge at a given pH
 If the pH is higher than the , the site is mostly deprotonated,
 If the pH is lower than the , the site is mostly protonated.
Strengths of Bases
 Strengths of bases are often expressed as of the conjugate acid,
o values are also used:
o
o
 Thus
o Where The auto-ionisation of water
Buffers
 These are solutions to which the additions of moderate quantities of acid or
base cause only minor changes in pH
o Most buffer solutions are mixtures of either:
 A weak acid and its salt with a strong base
 A weak acid and a weak base
 The Henderson-Hasselbalch equation is nearly flat near enabling
calculation of buffer pH
31
Example
 Estimate the pH of a solution containing 0.200 and
o Clearly is the acid and the base

 (tabulated data)
 ( )
o
 Initially and
 Let of liberated by dissolution to reach
equilibrium
 So at equilibrium:



 Thus
 Solving for x gives


32
9. Gases in Solution
Dalton’s Law
 The total pressure observed for a mixture of gases is equal to the sum of the
pressures that each individual gas would exert if it had alone occupied the
container at the same temperature
o
 Applying the ideal gas equation:
o
o Remember that is concentration so knowing partial pressures means
that you know the effective concentration
 The number of impacts is directly proportional to the
partial pressure
o Equilibrium gas solubility is proportional to
partial pressure
-3
1.2x10
Oxygen
-3
1.0 Nitrogen
Concentration/ mol dm
Helium
0.8
0.6
0.4
0.2
0.0
0.0 0.2 0.4 0.6 0.8 1.0
Partial pressure/ atm
 At equilibrium, the chemical potential of the gas in the solution must be
equal to the gas in the headspace
o For equilibrium (Note different species)
 Headspace:
 Solution:
 is mole fraction:
o

Henry’s Law
 This is commonly expressed as Henry’s Law
o
 The equilibrium concentration of dissolved gas in mole fraction is proportional
to the partial pressure
Methods of Expressing Gas Solubility
 1. Bunsen Coefficient, 
o Volume of gas reduced to 0 C and 760 mm Hg absorbed by unit volume of
solvent.
 2. Ostwald coefficient, L
o Ratio of the volume of gas absorbed to the volume of the absorbing liquid
all at the same temperature.
33
 3. Henry’s Law Constant, KH

o Allows prediction of the equilibrium constant of the dissolved gas
regardless of any following or coupled reactions, e.g. CO2, SO2, NH3 etc.
Henry’s Law Constant, KH
 Essentially this is the equilibrium for the reaction:
o
 For low concentrations, may be replaced by concentration (
 tabulations available in a variety of units
o ALWAYS CHECK THE UNITS
Example Table
 Various Henry’s Law constants at 25 C
o Here
Vapour Pressure of Water

 In calculating the concentration of
dissolved gas, account needs to be taken
of the vapour pressure of water
 Gas at the solution/gas interface is
saturated with water vapour
o
Worked Example
 Method
o Deduce the partial pressure of the gas of interest
 This may involve looking up the partial pressure of at the
appropriate temperature
o Check the units of
 Calculate the concentration of dissolved oxygen in water in equilibrium with air
at 25 C. Dry air is 20.95% O2. KH = 1.26  10-8 mol dm-3 Pa-1. The vapour
pressure of water at 25 C is 3167 Pa.
o and
o ( )
o
o
34
Temperature Effects
 Remember
 In the absence of chemical reactions, is negative for gases dissolving into
a liquid, thus must be negative
o However gases spontaneously dissolve so must be negative
 For low concentrations we can use the Clausius-Clapeyron equation:
o ( ) [ ]
 Salt concentration generally decreases gas solubility

Example
 The National Institute for Standards and Test supplies gas solubility data
through their webbook.nist.gov web site.
o The Henry’s Law constant for CO2 in water at 25 °C is given as 0.035 mol/
(kg bar).
o From the temperature dependence data, it is possible to deduce that the
Henry’s Law constant at 37 °C is 0.026 mol/ (kg/bar).
o What is the enthalpy of solution of CO2 over this temperature range?
 Recall the Van’t Hoff Isochore:
( )
o ( ) ( )
 Integrate to get
o ( )
 Henry’s Law constants can be treated as equilibrium constants:
o ( )
 Thus
35
10. Chemical Kinetics

 Thermodynamics only tells you what is possible
o Rates of chemical reactions affect all life processes
Reaction Rate
 For the general reaction:
o The rate of reaction, is the time derivative of the extent of
reaction divided by the volume:

o If the volume is constant, can be replaced by

Empirical Rate Equations

 For some reactions the rate of consumption or formation can be expressed
empirically:
o
o Where is the rate constant for the disappearance of A, and a and b
are constants giving the order with respect to each reactant
o a and b are independent of time
 The exponents a and b are partial orders of reaction
o The sum of the partial orders is called the overall order,
o The overall order need not be an integer for the total reaction
 As each reaction is made up of several steps
Order of Reaction
Zeroth Order
 When the rate is independent of reactant concentration, the reaction is
Zeroth order
o
First Order
 When the rate is proportional to the first power of one reactant only, the
reaction is first order
o
Second Order
 Second order reactions may be of the type where the rate law is of the form:
o
o For example:

 This is completely dissimilar to the balanced equation
suggesting a complicated pathway
 Another type of second order is possible where rate is given by:
o
o Here the reaction is second order with respect to X and second order
overall
36
Third Order and Higher

 E.g.
o The reaction is third order overall, second order with respect to NO and
first order with respect to oxygen.
 Higher reaction orders are less likely
Reactions with No Order: Enzymes

 Enzyme catalysed reactions frequently follow a rate law of the form:
o
 When substrate concentration the reaction is first order:
o
 At high substrate concentrations, the reaction is zeroth order
o
Determination of the Rate Law

The Ostwald Isolation Method
 Keep the concentration of all the reactants bar one in large excess (so that
their concentrations are effectively constant)
o If true rate law is and B is present in large excess then
o Where is the pseudo first order rate constant

o This greatly simplifies analysis
The Method of Initial Rates
 Suppose we have a reaction where all but reactant A are present in large
excess.
 The rate law will be given by:
o and at and
o
o
 Plot the logs of initial rates versus the logs of initial concentration for a
range of initial concentrations to deduce a.
 Initial rates are used as the reaction is far from equilibrium so the effect of
the backwards reaction can be ignored
Integrated Rate Laws
First Order
 The first order rate law for the consumption of reactant A:
o
o Rate
o
 At At t=t,
o ∫ ∫
o ( )
o
 This is first order for the fundamental reaction step
o Not necessarily an overall reaction rate law
 if ( ) is plotted against t, a straight line of slope –k is obtained
37
Half-life,
 The half-life of a substance is the time it takes for its concentration to fall to
half the initial value
 Substitute
o ( )
o
 Thus half-life is independent of concentration for a 1st order reaction
Second Order

o Rate =
o
 ∫ ∫


o Plot versus t to get a straight line, slope k
o The half-life of a second order reaction is proportional to

o Rate =
o
Considerations
 Similar expressions can be obtained for other reaction orders
 None of these expressions allow for reversible reactions so will fail as the
reaction approaches equilibrium
Example
 The metabolism and excretion of many drugs can be modelled as a first order
chemical reaction.
o 9 tetrahydrocannabinol is the principal active component in cannabis.
o Its measured half-life in plasma of 4.0 hours.
o Typical peak plasma concentrations are around 200 ng/ ml.
o Estimate how long it would take for a peak plasma concentration to fall
from a maximum of 200 ng/ml to 5 ng/ ml, where no acute effects are
observed.
 ( )
o

( )
o
38
Effect of Temperature on Reaction Rate

 Reaction rate, k is affected by the temperature
The Arrhenius Equation
 From a vast number of reactions it was empirically determined that:
( )
o Where
 is the rate constant (not the rate!)
 is the pre- expoenation factor
 is the activation energy
 is the thermal energy available to the system
Collision Theory – Incorrect Model
 Collision theory assumes that molecules must collide in order to react
 Consider reaction:
o Rate= ( )
 By subbing in Arrhenius equation
o As
 and so ( )
o Thus maximum rate would be which can be interpreted as
collision frequency
 The exponential term represents that fraction of molecules with
the proper orientation that have the energy to react.
 However kinetic theory of gases gives theoretical rate constants of
o But experimental values for simple reactions range from
Transition State Theory

 Considers the reactive intermediate (the species at the free energy
maximum) to be like a real molecule that lasts only a few bond vibrations
o The reactive intermediate is also known as the transition state or
activated complex
 Exists for only a few vibrations
 Very energetic
 Can switch to both product or reactant
39
The Model
 Assumptions:
o Rapid equilibrium reached
between reactions and
transition state(TS)
o Product formation is
inevitable once TS is reached
 Every elementary reaction
is rewritten as:
o
 The equilibrium constant can be
written by inspection
o
 The rate of formation of P:
o
 Combining the equilibrium constant, and the rate term:
o
 The experimental rate constant is therefore
o
 However and (note )
o ( )
o This is the Eyring Equation
 , so the Eyring equation expands to:
o ( ) ( )
o Therefore plot of vs. has a slope of –
o For most reactions is larger than giving

 ( )
Aside: Where does come from?

 Consider the transition state extending a certain distance along the reaction
coordinate
 The kinetic energy for this motion in 1D is given by:
o ̅
 Where m=mass of the transition state
 ̅ = average velocity
 Its de Broglie wavelength is given by:
o ̅
(as
 The transition state can be considered as extending over the range of (the
smallest possible energy state)
o The lifetime of the transition state, is the time needed to travel
o ̅ ̅
 The transition state decomposes into reactants or products
40
[ ]
o The change in concentration of P during the lifetime of the TS is
o The rate of formation of P is:
[ ]

 So by comparison with
o
Enzyme Catalysed Reactions

 Enzymes catalyse reactions- increase the rate but do not affect the position
of equilibrium.
o Enzymes are proteins but may have metal ions at the catalytic centre.
o May require low molecular weight co-factors
such as NAD, FAD.
 Highly efficient and selective catalysts
o Sensitive to pH, ionic strength and
temperature.
 Applications: drug targets, diagnostic tests, process
engineering, biosensors, DNA amplification.
 Typically several hundred kDa (
 Example: Glucose oxidase (Aspergillus niger)
catalyses oxidation of glucose to d-gluconolactone and
oxygen to hydrogen peroxide.
o Used in diabetic testing.
Example: Decomposition of Hydrogen

Peroxide

o Proceeds slowly without
catalysis
 Decomposition is usually first
order in the catalyst and substrate,
but for the catalase catalysed
reaction, the rate is zero order in
o Catalase is a hemoprotein with ferriprotoporphyrin (hematin) as a

prosthetic group.
 The reaction is hugely exergonic:  and should go to
completion if there is a suitable pathway.
o For uncatalysed reaction,
o With catalase, 
 The entropic barrier is reduced but the major effect is on the activation
energy.
41
 is larger than leading to catalysis

o An enzyme catalyses a reaction by
binding the transition state more
selectively than the substrate or
the products (Pauling (1948)).
o Adding product slows the reaction
down through product inhibition
 Rate of enzyme reactions is usually first
order for low [substrate] and zero order
for high [substrate]
o The catalytic constant or turnover
number is the maximum rate
divided by the concentration of
active sites.
Michaelis-Menten Kinetics
 V. Henri (1903), Michaelis & Menten (1913), Briggs & Haldane (1925).
o The enzyme-substrate complex is in equilibrium with the reactants.
 The FAST step
o The rate determining step is decomposition of the complex to yield
products P.
 RDS
o Simplest formulation neglects the reverse reaction between E and P to
reform ES.
 So good for initial rates that are not away from the equilibrium
 The fundamental reaction steps are:
o
 The rate of change of [ES] after an initial transient reaches a steady state
o (as [ES] is constant)
Formative Dissociative
 The steady state concentration of ES is therefore:
o
42
o
 The rate of the enzyme catalysed reaction is therefore given by:
o
 Un-measurable [E] is replaced with total enzyme concentration as
and
o
 Thus
Other Forms
 The maximum rate, occurs when
o i.e.
o Usual form of the Michaelis-Menten equation is:
 There are two important linear forms:
o Linweaver-Burk:
 Plot against
 Intercept with ordinate gives an slope is
o Eadie-Hofstee:
 Plot against
 Spreads the high substrate concentration data
 Conish-Bowden and Wharton (1998) produced a statistically unbiased method
o Calculated values of and are ordered and the median values are
obtained
Inhibition of Enzyme Reactions
Competitive Inhibition
 Competitive inhibitors:
compete for the active site.
o Enzyme can accept
either I or S.
Non-competitive inhibition
 Cannot be overcome by
increasing [substrate]:
 Can come about through:
o Permanent modification of
the active site
o Reversible binding of the
inhibitor to the enzyme, but
not in the active site
o Reversible binding to the
ES complex
43
Chemical Kinetics Summary

 Rates of reaction are measured by or
 Rates depend empirically on:
o Concentration
o Temperature (Arrhenius equation)
 Rate laws for fundamental steps can be written down by inspection.
o These can be combined (e.g. enzyme reactions) and compared with
experimental data.
 The temperature dependence of reactions can be explained by the fleeting
presence of a transition state.
o This explains how enzymes and other catalysts work; lowering the
transition state energy will increase the rate constant.
44
11. Steady State Heat Transfer

 Heat is energy in transit
o This occurs as a result of a temperature gradient or difference
o The temperature difference is thought of as a driving force that causes
heat to flow
 There are three main routes through which heat may be transferred:
o Conduction (Fourier's Law)
o Convection (Newton’s Law of Cooling)
o Radiation (Stefan-Boltzmann Law)
Conduction: Fourier’s Law

 A temperature gradient within a homogenous
substance results in an energy transfer rate within the
medium which can be calculated by:
o ̇
 Where heat transfer (W)
heat flux (W/m)
thermal conductivity (W/mK)
area ( )
temperature (K)
distance (m)
 This is random and is due to vibrations of
the constituent particles
o This means that solids are better
conductors due to their lattice
structures
o Diamond and graphene are also very
good due to high rigidity
Example in 1D
 The outside wall of a room is 4.5m x 5m. If the heat loss is 108
kJ/hr,
o What is the thickness of the wall?
o The inside and outside temperatures are 25 °C and -12 °C,
respectively and that the thermal conductivity of the wall
is 0.03 W/mK

o
( )
Conduction through multi-layered wall: The resistance network analogy

 System in steady-state
and no heat generated so
heat in= heat out
o
o
 By analogy with
where and
o
45
Example: Human Tissue

 Human skin consists of three layers, the epidermis, the dermis and the fat. Each
layer of skin varies in thickness at different points on the body.
o On average the epidermis is typically 1 mm thick, the dermis is 2 mm
thick and the fat layer is 7 mm thick.
o Thermal conductivity values for each layer of skin are 0.28, 1.5 and 0.73
W/ m K respectively.
o Calculate the heat flow though a 1 cm2 area of skin if the temperature on
the inside surface of the fat tissue is at 32 ºC and air temperature is -5 ºC.
o Assume good thermal contact between the layers of skin, homogeneity of
the skin and steady state heat conduction.
 Extract the facts and put them into suitable units
o
o
o Epidermis:
o Dermis:
o Fat:
 Consider the three layers and three resistances in series whose values are given
by per unit area.
o
 Consider now a steel rod implanted through the three layers that comprise skin
o Now resistance must be calculated for a parallel connection between the
three layers in series and the steel piece.
Multidimensional Conduction: The General Conduction Equation

 Basic principle based on First Law
o Energy conservation
 Rate of energy conducted into system
o
o
o
 Rate of energy generation inside system
o
 Rate of energy conducted out of system
o
o
o
 Rate of energy stored inside system
o
 So: ( )
o ( ) where
 α = thermal diffusivity (m2/s)
 k = thermal conductivity (W/mK)
 ρ = density (kg/m3)
 c =specific heat capacity (J/kg.K)
46
General conduction equation simplification

 Steady state no heat generation
o
 Steady state with heat generation
o
 Time dependent, no generation (NOT NEEDED for H+MT I)
o
Solving the General Conduction Equation

 Exact / Analytical solution
o Limited to simple geometries and certain boundary
conditions

 ∫ ∫

o Shape factor simplification valid for 2D medium
bound by two isothermal surfaces at T1 and T2

( )

 Approximate / Graphical solution
o Flux plotting, for insight only
 Numerical solution
o Finite different, finite elements or boundary
element method
o The most useful and appropriate method,
used on all level of complexity
Example: Ice-cream on a hot summers day
 2D time dependent model no heat generation
o ( )
 Initial conditions
o Material properties (k,ρ…)
o Initial temperature of the components
 Boundary conditions
o Insulator
o Heat Flux (i.e. Q = 100W)
o Surface
temperature
47
Natural Convection: Newton’s Law of Cooling

 The rate of heat loss of a body is proportional to the difference in
temperatures between the body and its surroundings
o
 Where heat transfer (W)
= heat transfer coefficient (
temperature (K)
o Heat is transported away by a fluid
 Again gases are worst for heat flow
compared to solids. Heat transfer
coefficient also depends on flow rate.
Combined conduction and natural convection
example
 How much heat is lost across the wall of a
house if the difference in temperature
between the inside and outside is 30 °C.
o Heat transfer coefficient for the
inside and outside walls are 20 and
10 W/m2K respectively.
o Thermal conductivity of the wall is 0.21 W/mK and thickness is 0.27m.
Convection Conduction Convection Convection Conduction Convection
1 2 3
1 2 3
 Individually:
o

o ( )

o

 ∑
o So
48
Radiation: Stefan-Boltzmann Law

 Radiation is the transfer of energy by electromagnetic waves
 All objects emit certain amounts of thermal radiation
o There is a thermal energy component to all EM radiation
o The level depends on the temperature of the body
 No medium is required and the energy transfer is highly dependent on
temperature
Properties and Definitions

 From the diagram:
o ρ = reflectivity, fraction of incident
radiation reflected
o α = absorptivity fraction of incident
radiation absorbed
o τ = transmissivity, fraction of incident
radiation transmitted
 α+ρ+τ = 1
o Solids and liquids: α+ρ = 1
 Most solids do not transmit
radiation, the only exceptions are
transparent or translucent solids
o Gases: α+τ = 1
 Most gases reflect very little thermal energy
Black Body: Ideal Receiver, Ideal Emitter
 A hypothetical object that absorbs all of the
radiation that strikes it. (α=1)
 It also emits radiation at a maximum rate for its
given temperature
49
The Stefan-Boltzmann law


o Where: heat radiated (W)
 ( )
o Body a is emitting heat radiation
o Body b is absorbing it.
 When bodies are heated why do they glow red orange….. then white?
o The object is getting more energetic and the frequency of radiation is
increasing, so they appear to us with different colours
Grey Bodies
 A grey body is a better approximation
of real surfaces. It allows us to relate the
radiation from real surfaces to that of a
black body.
o This is due to bonds and many
other non-ideal factors such as
wavelength dependence due to
bond absorption
Stefan-Boltzmann law for grey bodies
 Emissivity is important surface radiative
property.
o
o ( )
50
Further Examples
 One side of a 1m high by 2m wide vertical surface at 20 °C is exposed to
surroundings at 10 ° C. Assuming black body behaviour, what is the rate of heat
loss due to radiation?
o
 To make a more realistic estimate of heat transfer you now assume a grey body
behaviour, with the wall having an emissivity, , of 0.7, what is the rate of
radiation heat transfer now?
o
Putting it all together

 The hot gases in a furnace are separated from the ambient air and surroundings,
which are at 25 C, by a brick wall 0.15 m thick.
o Under steady state conditions, an outer
surface temperature of 100 C is
measured.
o What is the inner surface temperature of
the brick?
 The brick has a thermal
conductivity of 1.2 W m-1 K-1 and a
surface emissivity of 0.8.
 The free convection heat transfer
to the air near the surface of the
brick has a heat transfer coefficient
of 20 W m-2 K-1. The Stefan-
Boltzmann constant is 5.67x10-8
W m-2 K-4.
 We have an energy balance across a control surface at outer wall of furnace:
(First Law of Thermo: Energy Conservation!)
o
o So
51

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Haroon Chughtai

Heat and Mass

4. Entropy and the Second Law................................................................................................... 15

The Arrhenius Equation ................................................................................................................ 39

 If force is constant, and in opposite direction to direction of motion of object, this

Systems and Surroundings

 Exergonic: The system gives out energy

The Laws of Thermodynamics

The First Law

2. The First Law

 The system will compress is

Exact and Inexact Differentials

3. Heat Capacity, Enthalpy and Thermochemistry

Isobaric Heat Capacity,

 For some systems (e.g. monoatomic gases), is temperature independent

4. Entropy and the Second Law

The Second Law

Statements of the Second Law

Entropy as a State Function

Gibbs Free Energies of Formation

Chemical Potential and Equilibrium

o Pressure, temperature and moles of other species are held constant

 Thus the reaction will proceed to equilibrium where G is minimum:

 The ration is the equilibrium constant,

 Thus the Gibbs-Helmholtz Equation:

Temperature Dependence of Equilibrium Constants: Van’t Hoff Isochore

 Assuming is independent of T, and integrate:

Fick’s First Law

Fick’s Second Law

Example: Diffusion through a slab or flat membrane

o ( ) Integrate with x to get:

Average Distance Diffused in Time, t

o Hydrogen bonds are

 Electrostatic attractions are strong and long-range

The Bjerrum Length,

Solubilities of Ionic Solids in Water

Quantitative Approaches to Ionic Solubility

Calculating solubility from (and vice-versa)

Common Ion Effect

8. Ionisation and Acidity

o Clearly is the acid and the base

 3. Henry’s Law Constant, KH

Vapour Pressure of Water

 Salt concentration generally decreases gas solubility

10. Chemical Kinetics

Empirical Rate Equations

Third Order and Higher

Reactions with No Order: Enzymes

Determination of the Rate Law

o Where is the pseudo first order rate constant

Effect of Temperature on Reaction Rate

o But experimental values for simple reactions range from

Transition State Theory

Aside: Where does come from?

Enzyme Catalysed Reactions

Example: Decomposition of Hydrogen

o Catalase is a hemoprotein with ferriprotoporphyrin (hematin) as a

 is larger than leading to catalysis

Chemical Kinetics Summary

11. Steady State Heat Transfer