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Energy ʹ capacity to do work

Heat ʹ energy that flows

Temperature ʹ measure of internal energy

System ʹ defined as a quantity of matter or a region in space chosen for study

Surroundings ʹ mass or region outside the system

Properties: - Extensive: changes with extent of system, V.

- Intensive: independent of system extent, T.

Use of units: T (K) ; P (Pa) ; V (m3) ; m (kg) ; ni (mol) ; U, H (J) ; S (J.K -1)

Systems: 1- Isolated: matter and energy do not cross the boundary;

2- Adiabatic: heat does not cross the boundary;

3- Diathermic: heat can cross the boundary;

4- Closed: matter does not cross the boundary;

5- Open: heat, work and matter can cross the boundary.

Sign convention:

˜ SYSTEM 
Thermodynamic process: energetic evolution of a thermodynamic system proceeding from an initial
state to a final state.

Reversible (hypothetic): both system and surrounding can be returned to their initial states;

Irreversible (real process)

Isothermal: T1 = T2

Isentropic: S1 = S2

Isobaric: p1 = p2

Isochoric: V1 = V2

First Law: energy of an isolated system is conserved

U: internal energy ʹ state function (depends only on the system properties); we can͛t measure U,
only its variation:

‰         Isolated system:        U=constant


H: Enthalpy (state function)

H=U+pV Isobaric: Q=ѐH Isochoric: Q=ѐU

Lab conditions: ѐH = Qp

Enthalpy is not enought o predict the direction of a reaction;

Second Law: the entropy of an isolated system always increases.

Entropy ʹ a measure of disorder




Reversible process: ‰     ‰


Third Law: The entropy of any pure perfect crystal can be chosen as equal to 0 K. We can assign an
absolute entropy S = are tabulated and refer to standard conditions (R.T, 1 bar).

Factors affecting entropy: State ʹ gas >> liquid >> solid

Rigidity ʹ loose molecules > rigid molecules

Solution > pure solid + solvent (usually)

ѐSm, boil >>ѐSm, mel

The increase in the disorder is more importante when a pure compound is changed from liquid to gas
phase ʹ boiling ʹcompared to the solid to liquid change ʹ melting - .

Entropy does not decrease, only for an non isolated system that can happen (water turning into ice).

Stability of emulsion: thermodynamically unstable system consisting of at least 2 immiscible liquids,


one of which is finely subdivided and uniformly distributed as droplets throughout the other. The
system is stabilized by the presence of an emulsifying agent. The system evolutes spontaneously to
the phase separation. The protective agent (surfactant) only induces kinetic stability.

Degradation processes governed by the increase of entropy ʹ equilibrium state (2nd law).

Stability test: + cations (destroy the protective ʹ repulsion ʹ effect of the surfactant). Competition of
F1 (Van der Walls) and F2 (electrostatic repulsion due to the surfactant) will lead to degradation or
stability.

Gibbs energy (state function)

G=H ʹ TS T and P constant = ѐGsysч0

ѐGsys <0 : spontaneous

ѐGsys >0 : reaction will not go without help

ѐGsys = 0 : Equilibrium
At T and P constant the system goes spontaneously to na equilibrium state corresponding to dG=0 ʹ
direction of reaction ʹ tendency of evolution of a system is to lower the Gibbs energy.

Efffect of T and P

 
‰    ‰     ‰  ‰  ‰  ‰
   

Chemical potential: In a thermodynamic system of several constituents, the rate of change of the
Gibbs function of the system with respect to the change in the number of moles of a particular
constituent is the Chemical Potential.


   
  
!"

How much the free enthalpy (G) of a system changes (by dGi) if you add or remove a number of dni of
the particle species i.

Pure substance:

 #$%
       
   

n mols : G = nGm

Gm: molar
'
Perfect gas at T = cst &  & + RT ln p/p0

aGP = p/p0 = Activity

Pure substances: G=µ

Pure liquid/solid at T=cst.

'
&  &  #  ' %   &    ()*+)+,*(  & -&
'
   - '

Activity = 1 (pure solid/liquids)

Open system: ‰  . +  ‰ Fundamental Equation of Chemical Thermodynamics

Phase Diagrams

Boiling: L-G ; Melting: S-L ; Sublimation: S-G.


012 04
Dependence of µ with temperature: / 3  / 3   &
0  0 

P cst : dµ = -SmdT S is always >0 ; higher T : dT>0 ; dµ < 0.

The chemical potential of pure substance decreases with temperature.

S(s)<S(L)< S(G) µ = f(T) slopes = -S


Variance = independent parameters necessary to describe the system.

Gibbs Phase Rule: V = N ʹ r +2 ʹ Ø N: number of constituents:

r: number of relationships

Ø: number of phases

Vapor pressure: equilibrium with its condensed phase at a given T.

Boling point: vapor pressure = external pressure.

Critical point: vapor density = density of remaining liquid (Tc, pc) ; T>Tc : single uniform phase.

Melting point: given p, temperature at which the liquid and solid phases coexist in equilibrium.

Triple point: 3 different phases S,L,G coexist (lowest pressure at which a liquid phase can exist).
0
Clapeyron equation: 567  687 #7  6 %
0

Boiling - sublimation: slope (dp/dT) is always positive, except for water.

c   


A binary mixture is a mixture consisting of two components A and B. The composition is expressed in
terms of mole fractions XA and XB with XA + XB =1.

The concept of Partial Molar Quantities:

O   of a given component A is the volume contribution that the addition of one
mole of A makes to the total volume of a mixture A+B of a defined composition (XA, XB). The volume
occupied by a given number strongly depends on the molecules that surround them ʹ size,
interactions, etc. The same thing happens for enthalpy, Gibbs energy, etc.

So, changing the molecular environment of A and B results in a variation of the thermodynamic
properties of the binary mixture as its composition is changed, from pure A (XA=1, XB=0) to pure B
(XA=0, XB=1), the partial molar volume of A and B will vary with composition of the mixture.

General definition ʹ the partial volume Vm,I of a substance I at a given composition is defined as:

9
&  / 3 With ni number of mole of I; nj number of mole of other constituents hold

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constant.

The partial molar volume is the slope of the graph of the TOTAL volume as the amount of I is varied
Vtotal=f(ni), every other variable being constant.

Vm,I depends on the composition of the mixture. If the composition is changed by the addition of dnA
moles of A and dnB moles of B, the total volume of the mixture changes by:

dV = Vm,A . dnA +Vm,B . dnB


As V is a state homogeneous function, Euler͛s theorem can be applied, so that te total volume of the
mixture can be expressed as:

V = nA. Vm,A +nB. Vm,B

Partial Molar Free Enthalpy

The notion of molar partial quantity applies to any of the extensive state functions/ V, H, G, S.

Chemical potential ʹ partial molar free enthalpy:



1
  /
 3
" :;

Which means that the total free enthalpy of a binary mixture is given by:

G = nA. µ,A +nB. µ B<   .  =  

Gibbs-DuhemRelationship

nA. dµ,A +nB. dµB = 0 or.  > ‰   

Chemical potentials of a mixture can not change independently:

For a binary mixture: 6 ? 7 @

Using the Gibbs-Duhem relationship for a binary mixture allows the determination of a partial molar
quantity provided that the other is known. True for any quantity Ym,I (not only forµ):
0B
.  > ‰A&   With A&  / 3T,P,nj
0"

So with Y=Total volume ʹ Gibbs Duhem relationship:

6
6 > ‰&6    7 > ‰&7    ‰&7     > ‰&6
7

In a binary mixture, if a partial molar volume increases, the other must decrease. Molar volumes are
always >0 but the corresponding partial molar volume may be >0 or <0.

Partial molar quantities at infinite dilution.

For a binary mixture: A+B.

XA ї1: the substance A becomes essentially pure. So that Ym,A їY*m,A: molar quantity of pure A.

But XBї0: the B substance becomes close to infinite dilution. YM,B ї YCM,B: partial molar quantity at
infinite dilution in A.

The Chemical Potential of a Liquid


The chemical potential of a substance is the same in all phases at equilibrium (second law of
thermodynamics); the chemical potential of A in a liquid mixture (A+B) at eauilibrium is eauql to the
chemical potential of A in the vapour phase.

Ideal Solutions

For a pure liquid A, the chemical potential µA(L)* is equal to the chemical potential of the
vapour A, µA(gaz), which is in equilibrium with the liquid at a give T. The corresponding pressure of A
is the saturated vapour pressure o the pure substance, noted pA*.

µA(L)* = µA(gaz)

µA(gaz) is the chemical potential of a perfect gas at a given T and p which is equal to pA*. In
these conditions:

µA(L)*=µA° + RTln(pA*/p°)

Partial pressures

Chemical potential of a perfect gas: µGPT,P=µT° + RTln(p/p°)

In a gas mixture: µGPA =µA° + RTln(pA/p°), where pA is the partial pressure of A in a mixture of gas.

Dalton͛s Law of partial pressures: The partial pressure of an ideal gas in a mixture is equal to the
pressure it would exert if it occupied the same volume alone at the same temperature. This is
because ideal gas molecules are so far apart that they don͛t interfere with each other.
D =E D
6   = G G H." "
9 F

In a mixture A+B liquid, the chemical potential of A is equal to the chemical potential of A in the
vapour phase which is now in equilibrium with the liquid at a partial pressure pA which is now тpA*.

µA(L) = µA(gaz) Always true!!

µA(L)=µA° + RTln(pA/p°) µA(L)=µA*(L) + RTln(pA/pA*); Where aA(L) = (pA/pA*);

Raoult͛s Law states: the vapour pressure of an ideal solution (pTOTAL) is dependent on the saturated
vapour pressure of each chemical component (pi*) and the mole fraction of the component in the
liquid phase (Xi(l)) present in the solution. Once the components in the solution have reached
chemical equilibrium:

PA=XA .pA* = pAid,* IDEAL SOLUTIONS µ A(L)=µA*(L) + RTln(XA) = µAid,*

in a pure liquid, some of the more energetic molecules have enough energy to overcome the
intermolecular attractions and escape from the surface to form a vapour. If you have a second liquid,
the same thing is true. In an ideal mixture of these two liquids, the tendendy of the two different
sorts of molecules to escape is unchanged: P=XA .pA*+ XB . pB*.

Some mixtures obey Raoult͛s Law very well, especially if the components of the mixture are
structurally similar. Mixtures which obey the law at all compositions; from pure A to pure B, are
called Ideal Solutions. Most liquid mixtures do not show an ideal behavior, but very often; Raoult͛s
Law is obeyed for the component in large excess, the solvent.

Henry͛s Law

In most cases, the vapour pressure of the minor component, B ʹ the solute, is not proportional to irs
saturated vapour pressure PB*, so the Raoult͛s law is not obeyed. However, as long as B is at low
concentration in the A+B mixture, a linear dependence of the vapour pressure pBwith the
composition (in the liquid phase) XB is found:

PB = KB + XB, where XB is the composition of the liquid phase and KB is the Henry͛s constant,
which is determined as the slope of the tangent to the curve p=f(XB) at XB=0.

When the solute B obeys the Henry͛s Law (XB = pB/KB), the chemical potential of B is:

µB(L)= µBC(L) + RTlnXB ʹ Chemical potential of B in an Ideal Dilute Solution.

Non ideal solutions

Most of mixtures have a non ideal behavior.

Deviation from Ideal Dilute Solution, the chemical potential of B is:

µB(L)= µBC (L) + RTlnXB+ RTlnI B = µB(L)= µBidC + RTlnIB

IB: activity coefficient ref C

IB. XB = aB: acitivity of B in the mixture, referring to C

For the ideal dilute mixture: IBї1 and aB їXB.

For a real mixture: XBї0, I Bї1. The solute follows Henry͛s law when it is very diluted.

Deviation from ideal pure liquid state *:

The chemical potential of B can also be expressed by:

µB(L)= µB*+ RTln(fB.XB) = µB*+ RTln(XB) + RTlnfB = µBid* + RTlnfB

fB: activity coefficient ref *.

fB.XB: activity of B in the mixture, referring to the pure substance *.

For the ideal pure liquid: fBї1 and aBїXB.

For a real mixture when: XBї1, fBї1. The solvent follows Raoult͛s Law when the solute is very
diluted.

Applications

The partial vapour pressure and olfaction: the vapor pressure leads molecules to transfer from the
liquid to gas state. The more important the partial pressure is, the more volatile the compound is.
The vapor pressure decreases as the molar weight and the boiling temperature increase
Volatility and relative Volatility ʹ application to aromas.

͚I͛ is a compound in a non ideal mixture with A,B,͙(other compounds), with the following mole
fraction in the liquid phase Xi, XA, XB, ͙the partial vapor pressure of I is influenced by the presence of
other compounds:

Pi = pi* .fi . Xi With pi* being the saturated vapor pressure of i.

fi: activity coefficient of i: deviation from the ideality (ref Raoult) which takes into account the
repulsion strengths between molecules of solute, interactions between solute and solvent.

With p=total pressure, considering the gas as a perfect gas, the mole fraction of I in the fas phase, yi,
is expressed by:

(With pi=yi.p so yi=pi/p) yi = fi.Xi.pi*/p so yi/Xi = fi.pi*/p

Odorant molecules being present in a very weak proportion in mixtures, we can consider that the
compound I (aroma) is very diluted in the mixture and so obeys the Henry͛s law:

So that pi = Ki.Xi fiC.pi* = Ki : Henry͛s constant.

Relative volatility: is a measure comparing the vapor pressure of the components in a liquid mixture
of chemicals. This quantity is widely used in designing large industrial distillation processes. In effect,
it indicates the ease or difficulty do separate the more volatile components from the less volatile
components in a mixture. It is a measure of the differences in volatility between 2 components. I
indicates how easy or difficult a particular separation will be. The relative volatility of component ͚I͛
with respect to component ͚j͛ is defined as:

#K ML % N >  O


J:  
#K: ML: % N: > : O

Where yi is the mole fraction in vapor phase and xi is the mole fraction in liquid phase.

If the relative volatility is very close to one, it is an indication that they have very similar vapor
pressure characteristics. This means that they have very similar boiling points and therefore, it will be
difficult to separate the 2 components via distillation.

For odorant molecules and aromas, it is interesting to define the relative volatility of I compound
against that of water:


N >  O
JP 
NPQRST > PQRST O

ɲiwis the equal to the ratio of Henry͛s constant of aromas and water. The most important ɲiw is, the
most volatile is the aromas in the aqueous mixture. The most important is the olfactory stimuli.