( )

f 1(T ) **If P real > P ideal, we conclude that the repulsive interaction is more
important than the attractive interaction. If Preal < P ideal, attractive Tf Ti
Boyle’s law: V = ; Charles’s Law: V = f2(P)T ; PV=nRT
−nR P Ext
ΔU = nCmV (Tf -Ti) = -PExt (Vf -Vi) = −
P dominate. **
Redlich-Kwong Equation: Pf Pi
Assumptions:

( )
2
1) Atoms/Molecules do not interact with each other nRT a n R P Ext
2) Atoms/Molecules can be treated as point masses P= − =
C mV +
Pascal Pa 1Nm-2 = 1 kg ms-2 V −nb √ T V (V +nb) Pi
Atmosphere atm 1atm = 101325Pa RT a 1 T f =T i
− R P Ext
Bar bar 1bar = 105Pa
V m−b √ T V m (V m +b) C mV +
Torr or millimetres of Hg Torr 1Torr = 101325/760 =133.32Pa f
Pf
Pounds per square inch psi 1psi = 6894.8Pa State function U: ΔU = ∫ dU=U f −U i Heat Capacity: JK-1/ Total Heat
dQ dQ dQ
The Carnot Cycle : (Carnot’s Theorem: = 1 -f(Th, Tc)
1. Reversible isothermal expansion (Th) ΔU=0 : Qhot : tve
;C =( ) ;C =( ) ;C
R value i C= V P TOTAL = nCm Cp > Vb Vb
8.31447 Jk-1mol-1
dT dT dT P nR T
8.20574 X 10-2 dm3 atm K-1mol-1 Cyclic path: ∮ dU =U f −U i=0 CV
V
Wab = − ∫ PdV = −∫ h
dV =
8.31447 X 10-2
8.31447
dm3 bar K-1mol-1
Pa m3 K-1 mol-1
First Law of Thermodynamics: U of an isolated system is constant T2 Va Va
V
∆ U Total =∆ U System + ∆U Surroundings∨¿
162.364
1.98721
dm3 Torr K-1 mol-1
Cal K-1 mol-1 (1 cal = 4.184J)
Q=
∫ CdT = C (T 2 -T1) specific heat capacity of water = 4.18Jg- Vb
−nR T h ln ( )
Dalton’s Law for ideal Gases: PTOTAL = PA + PB + ….. = ∑Pi (Partial ∆ U System =−∆ U Surroundings T1
Va
1
Pressure) du = dQ + dW (closed system) | dU = dQ +dW +dUmatter (open system) K-1
Vb
ni RT nTotal RT ni U U
( )
Force (Extended Spring):
( ) dT +[ + P]dV ΔUab = 0 = Qab +Wab => Qab = -Wab = nRThln ( )
Pi = | P = ∑P = TOTAL i | Xi =
∑ ni
| n=
f ex =−f spring =k ( y− y 0) dQ = dU + dW = dU – PdV =
T V V Va
V V x2 x2
T

( )
2. Reversible adiabatic expansion (Th > TC) [
∑ ni = n + n + …. U
A B
w=∫ f ex d ( x− x0 ) = ∫ k ( x−x 0 ) d (x−x 0) CP – CV = [P + ¿ ¿ nR or C mP -CmV = R γ
P V =P V =PV ¿
γ γ
∑ X i = X + X + …. = 1 | P = X P |
A B I i Total x1 x1 V T
b b
Vc
c c
Vc γ
PA + PB +…. = XAPTOTAL + XBPTOTAL + …. = PTOTAL (XA + XB + ….)
1 For ideal monatomic gases: CmV = 3/2R ; For diatomic gases: CmV = 5/2R P V −P c V c γ V c 1
=PTOTAL =
2 2
k [ ( x 2−x 0 ) − ( x1 −x0 ) ] ; k =Nm -1
, w =J, x =m QP = nCpm (T2 -T1) & QV = nCVm (T2 -T1) W =−∫ PdV =∫
bc
b b
γ
dV =
Lennard-Jones Potential Energy 2 Adiabatic process:
( γ −1)
Vb V Vb
Work due to Volume Change: TV =constant A P c V c −P b V b nR(T h−T c )
Work done against vacuum = 0 => Pext = 0
W (tve) => surroundings are doing work on the systems (P ext > P) C mP = = or =ΔU =
W (-ve) => systems are doing work on the surroundings (P > Pext)
γ
P V =constant B , where γ = 1−γ γ −1
Reversible Process: A process during which the system is never more than C mV nCmv( Tc -Th)
infinitesimally far from eqm [Pex = P-dP at all times during expansion] γ 1−γ 3. Reversible isothermal compression (Tc) ΔU=0 : Qcold : -ve
Isobaric Gas Expansion (irreversible): Pex ≈P T P =¿ ΔUcd = 0 = Qcd +Wcd => Qcd = -Wcd = nRTh

( ) ( )
V2 V2
Cmp Vd Vc
w=−∫ Pex dV = −∫ PdV = −1 ln =−nRTln( )
T f −γ −1 Pi C mp−R P Vc Vd
σ 12 V1 V1
ln = ln = ln i
ULJ(r) = 4ɛ [( ¿ ¿ −¿ ] 4. Reversible adiabatic compression (TC > Th )
r −P ( V 2−V 1 ) =−nR ( T 2−T 1) Ti γ Pf C mp Pf
Pd V d−Pa V a nR(T c −T h)
Van der Waals Equation (1dm3 = 10-3 m3 = 1L) Isothermal Expansion (reversible): Pex ≈P
C mp−R W da= =¿ or =ΔU =
nRT
2
n a
2
n a nRT
V2 V2 V2
1−γ γ −1
P=
V −nb V
− 2 or (P + 2 ) (V-nb) =nRT w=−∫ Pex dV =−∫ PdV =−∫ dV Enthalpy: H = U + PV ; ΔH = ΔQp & H= Q (at constant pressure) nCmv( Th -Tc)
V V V V
V T2 Valid under
Overall analysis: Wcycle = Wab + Wbc + Wcd + Wda = - (Qab +Qcd)

∫ C V dT =¿ ¿
1 1 1 condition,
nRT 2 RT 1 When V is constant: ΔU = QV = CVregardless
(T2 -T1) Vb Vd
−P ; P=a( n ) ; P =
V
− 2a ¿−nR T c ln( ) =
V m−b V m ¿−nRT ∫ 1 dV ¿−nRT ¿
2
P= reversible or not = -nRTh ln (
T1
V −nb V Va Vc
V T2

( ) ( )
V
P ❑
2
P ∫ C P dT =¿¿ Vb
1
When P is constant: ΔH = QP = CP (T2 -T1)
At critical point: =0 =0 , Max work that can be −nR ( T h−T c ) ln
V T V T
2
extracted from a process btw T1 Va
same initial and final states is ΔH = Δ(U +PV) = ΔU + Δ(PV)= ΔU(T) + Δ(nRT)

We obtained: a =
9
R T C V mc b =
V mc
T=
8a
P =
that obtained under reversible ΔH = ΔH(T) =n(CmV +R) ΔT = nCmp ΔT
For isobaric expansion: Efficiency:  =
|W cycle| = T h −T c =1− T c =
conditions (area under the
c

8 3 27 Rb graph) ΔU = qP +wP = nCp (T2 -T1) +[-nR(T2 -T1)] = n(Cp -R)(T2 -T1) Qab Th Th
For real substances (shomate equation): CmP = A+BT+CT2+DT3+E/T2
a Adiabatic, constant external pressure: Qab+ Qcd Qab Qcd
2 V =3b
mc
W=mg (h2-h1) ; ; + =0
27 b W = I  t => It =Q Qab Th Tc
QV =W
Refrigerators: ¿−nR[ X A ln ( X A )−X B Rln ( X B ) ] 25℃=298.15 K (Eqn valid only when there is no ∆ in f
Q =k = ; ∆ G 0 =−RTlnK=∆ H−T ∆ S (find T
C r= cold =¿ Qcold ∨ ¿
Extensivity of Entropy:
¿
phase for rxn)
c¿¿
∆ G=∆ H−T ∆ S ; aA+bB → cC
[ ]
Gibbs Free energy:

( )
W T cold
|Q hot|−¿ Qcold ∨¿= T −TS ( V ,T
hot cold
¿ , n )=n S 0+ Rln V +C mV ln(T )
n
+dD

0
∆ G =−RTlnK ; ∆ G=∆ G + RTlnQ; Q=
0
=
c ( ∆H
∆ ]S−RnK
[C ] [ D d
, k∆ c ¿
)
dQreversible dQreversible Entropy Changes in phase transformation: Example
a b of Ss and loop
Entropy: ∮ =0 ; dS= [ A ] [ B↔
[SS]] [H] K1 ; 2[SS] ↔ [DS] K 2 ; [SS]+[H]+2[DS] = c
T T [SS]+ K1 [SS] + K2 [SS]2 => Let x = [SS] and solve
S = klnN => eS/k = N [no. of microstate of the system] vaporization
Thermodynamics characterization of protein stability
=>liquid to
**k = 1.318 X 10-23mol-1, R=kAvogadro (6.0 X 1023mol-1)
gas N (Native State) ↔ D (Denatured State)
dQ fusion=>
fA '
The Clausius inequality: dS ≥ ΔS must be calculated along solid to KA = => fA’ +fA = 1 (assume protein made up of no. of domains
T liquid fA
a reversible path. Because S is a state function, ΔS is necessarily path
A,B)

[ ]
independent, provided that the transformation is between the same initial
¿
and final states in both processes. • If the process is irreversible, we must dQreversible Qreversible ∆ HStructure of ATP(adenosine triphosphate: Nucleotide with unstable K
K A ∆ C pA K A ∆ H A ∆ H A
=∫
vap that the cell hydrolyse for energy to drive endergonic rxn. (adenine,
find an equivalent reversible process for our calculation. ∆S Vaporization =¿ = ribose,¿3 phosphate grps) ATP + H20 -> ADP +Pi ΔG = -31kJ/mol
bonds
C p=C pN + + +…
Reversible isothermal expansion or compression: T T vaporization T vap
Temperature dependence of Equilibrium constant (Van’t Hoff Eqn):
1+ K A 2
( 1+ K A ) R T 2

[ ( )]
ΔU = 0 => Qrev = -Wrev => (same for fusion) 0
Vf Vf ∂ ( lnK ) −∆r H C p ( T )=B0 + B1 T +¿
W rev =−nRTln =¿ Qrev=nRTln =
Vi Vi 1 R => ∆ H A (T )=∆ H mA ( T )+ ∆ C pA ( T −T mA )
∂

{
Q rev Vf Pf T P
( ) (
∆ S= =nRln =−nRln −∆ H mA T ∆ C pA
T Vi Pi K2 0 T2 K A =exp 1− − T −T m
−∆r H 1 RT T mA RT
Reversible change in T at constant V:
Tf Tb
∫ dlnK = R ∫d T
dQ reversible nC mV dT Tf C P ( s ) dT ∆fus H C ( l ) dTK ∆ vap H T
∆ S=∫ =∫ ≈ n C mV ln S ( T )=S ( 0 ) +∫ +∫ P
1 1
+ + K
( )
0
T
Constant pressure process:
dQ reversible
T

nC mP dT
Ti

T f +∫ P
T
C ( g ) dT
0
T Tf T f
T
ln
K
T2b = −∆r H 1
1 R (T 2
−
1 *since
T 1
) 0
∆ r H is
(3 law of thermo states that the ∆ S of a pure, independent of T, find ΔH
∆ S=∫ =∫
rd

≈ n C mP ln T 0 0 0
T T T
T i perfectly b
crystalline substance is 0 at 0K)
∆ r G =∆r G ( Initiation ) +∑ ∆ r G ( nearest neighbours )
Any reversible or irreversible process : 0 0 0
Entropy Change of a Chemical Reaction: ∆ r S =∆r S ( Initiation ) +∑ ∆r S ( nearest neighbours )
Vf Tf n A A+ nB B →n C C +n D D ; Protein-DNA Interactions
Given (V & T ) => nRln +nC mV ln 0 0 0
∆ r H =∆r H ( Initiation ) +∑ ∆r H ( nearest neighbours ) [M • L]
S S

Vi Ti ∆ r S=n C SC +n D S D−n A S A −nB S B 0 M +L ↔ M•L ; fraction of bound sites: f =

Pf Tf 0 0 ∆ r G ( Initiation ) =+8.1 kJ /mol ; M
[ M ] +[ M • L]
Given (P & T ) => −nRln +n C mP ln ∆ S R =∑ v i S i (Vi positive for products, negative for 0
S S
Pi Ti reactants) ∆ r S ( Initiation ) =−23. 4kJ/mol/K; [ M • L] [ L] K ;
Eqm constant: K = ;: f =
Entropy: Temperature Dependence 0
For reversible system Total ∆ S=0 ,For irreversible Total 0 0 ∆ r H ( Initiation )=+ 0.8 kJ /mol [ M ] [ L] M
1+[L] K
∆ S ( T 2 )=∆ S ( 25℃ ) +∆ S A ,T 2 → 25℃ + ∆ S B , 25℃ Amt of bound ligand as function of f : [L] = [L]+f [M]
∆ S> 0 → T 2 of dna double strand:
Example M Total M Total

[ ]
( [ ]
)
[ L ] Tot
For isolated system ∆ S (isolated systen)≥ 0
25 ℃
dT
T
2
dT 2S↔ D ; f = 2 D fc 2 1 L Tot
=∆ S ( 25 ℃ ) + ∫ C
0
+¿ ∫ P, B T
C ¿ => [D] = => k= f −f + +1 + =0 ;
For sum of entropy P ,A
T C 2 M M
[ M ] Tot K [ M ] Tot [ M ] Tot
T 25 ℃
∆ S ( system )+ ∆ S ( surroundings ) ≥ 0 2
c Total heat produced (Q) for binding a fraction of sites fm:
T
dT
2 T 2
dT f( ) f
Mixing of 2 gases: (no entropy change when mixing two identical gases) 0
=∆ S ( 25 ℃ ) −
∫ C P , A T +¿ ∫ C P , B T ¿ 2 = [ D ] 2 = Q=f M ( [ M ] Tot V 0 ) ∆r H
0

2 2c¿¿
25℃ 25 ℃ [ S ] [c ( 1−f ) ] V = initial volume of biomacromolecule soln
0

Pf
( )
X AP T Ionic Effect on Protein-DNA interactions
dT c
2
+ ¿¿
∆ S A =−n A Rln =−n A R =−n A Rln(X 0) P+L ↔ PL+ χψ Na ; K=(α ¿¿ PL)¿ ¿ ¿ ¿ [L]: conc
Pi P =∆ SA ( 25 ℃ ) +
∫ (C P , B−C P , A ) T S + S ↔ D ; [S ] + [S ] = (1−f ) =>
1 2 1 2
2 of protein, M ; [P]: conc of DNA, mol phosphate/L ; [PL]:conc of complex, M
25 ℃
[ PL ]
∆ S B=−nB Rln =−n B R
Pf
Pi ( )
XB P
P
=−n B Rln (X B )
0
=∆ S ( 25 ℃ ) +
T 2
dT k =
∫ ∆ C P T => ∆ C P is the difference [ S 1 ] [S 2] c
[D ]
=
f (c /2) K obs =
[ P ] [L]
; therefore K obs =K ¿ ; assume

( )
2

∆ S mixing=∆ S A + ∆ S B=−n A Rln ( X A )−n B Rln of( XCpBof)∨¿ 25 ℃ (1−f ) ψ=0.88

P and R 2
One component Systems Two component systems:
RT w aA + bB →cC + dD ; rate of rxn =
Clapeyron Equation : dG =VdP – SdT ; V&S always +ve (For binary, liquid/liquid soln) Raoult’s Law: π= nB =cRT = RT w =conc in kgm-3, M = MW
PTotal = XA P0A + XB P0B = XA P0A + (1- XA )P0B V M −1 ∆ [ A ] −1 ∆ [ B ] 1 ∆ [ C ] 1 ∆ [ D ]
Dissolved solute lowers vapor pressure of solvent. This results in boiling point
in kgmol-1 = = =
elevation. Freezing point is also affected and is lowered. Higher vapour pressure
Example of osmotic pressure: Conc = Density / MW a ∆t b ∆t c ∆t d ∆t
means lower BP. m n
Rate of rxn = k[A] [B] ; overall rate of rxn = m+n, k= Aexp[-Ea/RT]
Example of lowering water vapor pressure 2 C
3 OH COOH ↔ C OH 2COO + H 3
- +

−d [ A ]
PV ,B Assume complete dissociation: π=2 cRT Zero order: =k => −∫ ¿ =>[A] = [A] -kt t 0
Henry’s Law Coefficients k = B
XB
(x= solubility of gas)
Assume no dissociation: π=cRT ; % dissociation = dt ¿¿
−d [ A ]
PN 2 P O 2 P Ar Given P−zero d P First order: =k [ A ] => ∫ ¿ => ln ¿ ¿
X air =X N + X O + X Ar= + + ; zero d P
x 100 dt ¿¿
2 2
k N 2 k O 2 k Ar ln 2 −d [A] k
0 0 0 K =[ Py ] ¿ ¿ ; pk = -logK Half life = t = ; Pseudo order: =¿
∆ P H 2 O=P H 20−P H 2 O=P H 20 ( 1−x H 20 )=P HBasic 20 xConcepts
air in electrochemistry: k dt
1/2

m ; assume ( ∂ T ) =¿ to
3
M Dalton Law: P A =γ A PT
2+ 2+
Zn(S)| Zn (aq) || Cu (aq)| Cu(S) => E cell = E red - E ox 0 0 0

Vm (molar Volume)= = More -ve => oxidize, more +ve => reduced
ρ mole ∂P f Example of Henry Law- Solubility of gas in solution:
solve T or P Most gases are less soluble in water as T increases; organic solvents is
reverse 0 0 RT 0 RT
PV ,B nB ∆ r G m=−v e FE ; E=E − lnQ ; E = lnK
Triple point
x =
B = , because n << 1, B
ve F ve F
temp=
273.16K
kB nB +n Solvent , F=96485
Transmembrane Equilibria: (energy requires to transport Q across
Assumptions:
n B +n Solvent =n Solvent mem)

1.Vg >>Vl; ∆ V =Vm,gass -

vap nB RT ∆ r Gm=ZFV =∆ μ E; Z = charge of ion ; V= transmembrane
Vm,liquid ≈Vm,gass n =n
B ×x ;V =
solvent B B ; n = change of B moles from H-P to potential
B

P
∆ μC =∆ μ + RTlnQ ; ∆ μ=∆ μ E +∆ μC ¿= 0 for
2. Ideal Gas Pv=nRT 0
Low P
3. ∆H is independent of

[ ]
vap
0 membrane)
α B2 −∆ μ B −RT
Partition Equilibria: =exp ;
ZFV ¿−RTlnK ;V = lnK ;
Vapor-liquid Equilibria : α B1 RT ZF

( )P vap 2 −∆ vap H m 1 1
( )
0 0
ln = − ∆ μ B =∆ GB /mole ∆ pH=lo g10 ¿ ;lnQ=2.303(∆ pH ¿
P vap 1 R T2 T1 v
Colligative property: depends on the no. of particles present Equilibrium Dialysis : =K ( N−v) =>
Clasius-Clapyeron Equation-modification: ∆ H is NOT independent Vapor Pressure is lowered when a solute is present: Boiling point
vap
elevation, Freezing point depressed (Pressure &Temperature graph)
[ A ]
of T&P but vary linearly with T
v=[ A] inside−¿ ¿
0.018 kg
M= for water m 2/ Mno.A= small molecule, v=no. of bound A molecules per macromolecule, N=
2of binding sites on macromolecule, [M] = conc of macromolecules
mol ∆ T f =−K f × m; ∆ T b =K b ×m; m=
0 0 1000 g Effect and Donnan Potential: C = C =C
Donnan Na,out cl,out

∆ vap H=∆vap H +∆ vap C P (T −T ) 0 m1/( C –)C +Z C = 0 ; at eqm : μ Na,∈¿=μ , μ

kg Na,in cl,in M M ¿ Na ,out cl ,∈¿=μcl ,out ¿

1= solvent, 2 =solute ∆ μ Na =μ Na ,∈¿− μ = FV + RTln¿ ¿(for cl, -ve FV)

( )
0 0 Na,out

( )
P vap 2 (∆¿¿ vap H −∆vap C P T ) 1 1 0 ∆ vap C T 0
FV =−RTln ¿ => RTln ¿
ln =− − 0 +Moles ofP A ln( 0 )¿ Moles of solute Moles of solute
P vap 1 R T xTA= R ; m=
T ;M
(C
=C ) =(C C ) = C =>
Na,out cl,out Na,in cl,in
2

Example of water vapor: kg of H2O evaporated=

Total moles Mass of Solvent (kg) C Volume of Solution (L)
−Z C + √ ( Z C ) +4 C
2 2
M M M M
FP/ BP Depression: Na ,∈ ¿= ¿
Js−1 m−2 × s ×m 2× kg /mol 0 0 0
2

√
J /mol ∆fus H ∆ fus H (T f −T )
∆ fus S =
0
;∆ μ =
0
C Na,∈¿ −Z M C M ZM CM 2
nRT Tf
0
Tf
0 r=
= + ( ) +1 ¿ ; K+,
V= => n= mass/ M ; P =vapor pressure at that temp.
fus
C 2C 2C
P M1 m Na+ => r <1 , Cl- => r>1
x = ; (T ¿¿ f ¿¿ 0−T )=R ¿ ¿ ¿ ¿
Final vap P 2
1 kg −RT C Na ,∈¿ −RT
Mass of rain = (1- ¿ ×mass (kg); Heat release V= ln = ln (r )¿
initial vap P RT F C Na, out F
Osmotic Pressure: P = ρ hg ; π= n (in dilute soln,
mass of rain n A V mA B
= × ∆H vap

M n A V mA=V ¿