Generalization of Ideal Gas Behavior Boyles Law The volume of any definite quantity of gas at constant temperature varied

inversely as the pressure on the gas.  P1V1 = P2V2

Ideal Gas Equation  PV = nRT

Values of R:

0.08205 L-atm/mol-K 82.05 cc-atm/mol-K

Charles Law The volume of a definite quantity of gas at constant pressure is directly proportional to the absolute temperature.  

8.314 x 107 ergs/mol-K 8.314 J/mol-K 1.987 cal/mol-K 62360 mmHg/mol-K

Gay-Lussacs Law  

Daltons Law of Partial pressure At constant temperature, the total pressure exerted by a mixture of gases in a definite volume is equal to the sum of the individual pressure without each gases would exert if it occupied the same total volume alone. PT = P1 + P2 + P3 + +Pn Partial pressures: P1 = P2 = P3 =

Combined Gas Law   

Avogadros Law  

Daltons Law: PT = PT = nT  

VB/V = NB/RT = NB VC/V = NC/RT = NC

Graham's Law of Diffusion Partial Pressure of a gas pressure of the mixture: P1 =  P2 =  P3 =  to the total At constant temperature and pressure, the rate of diffusion of various gases varies inversely as the square roots of their densities or molecular weights. = Where: u or r p1 or p2 Amagats Law of Partial Pressure In any gas mixture the total volume may be considered to be the sum of the partial volumes of the constituents of the mixture. VT = V1 + V2 + V3 + + Vn V = V = (n1 + n2 + n3) nT If: Limitation of Ideal Gas  Low to moderate pressure PV = znRT Where: z = compressibility factor z > 1 = dominant adhesive force z < 1 = dominant cohesive force = = rate of diffusion densities =

PA/PT = nA/nT = NA PB/PT = nB/nT = NB PC/PT = nC/nT = NC NA + NB + NC = 1

(mole fraction) (mole fraction) (mole fraction)

VA/V = NA/RT = NA

Van Der Walls Equation of State Van Der Walls deduced that the magnitude of the pressure correction P' for n moles of gas present in volume V is given by: P' = Thus: (P + (V-nb) = nRT where a is a constant

Berthelot Equation PV = nRT (1 + Where: 

T = actual temperature Tc = critical temperature P = actual pressure Pc = critical pressure

Note: valid only for wide pressure range a = b =

Beattie - Bridgeman Equation of State P = Vm = Where: = RTB0 - A0 = -RTB0b + Aoa = T = absolute temperature R = gas constant Ao, Bo, characteristic a, b, c of each gas = constant    
 

 

Kamerlingh Onnes Equation of State  PV series PVm = A + BP + BP2 + BP3 + Where: P = pressure Vm = molar volume A,B,C = viral coefficients Rate: PVM = A PV2 = nRT

Molecular Weights of Gases p = MW = p = M = > based upon the fact that as zero pressure is approached, the ideal gas laws become the exact for all gases Some Methods for Determination of Molecular Weights Regnult's Method > employed to determine the molecular weights of substances which are gaseous at room temperature. Dumas' Method > used to determine molecular weights in the vapor phase of readily volatile liquids. Wvapor = W(bulb M =
+ vapor)

Determination of Exact Molecular Weights Method of limiting densities

PMW = pRT p/P = MW/RT = constant (p/P)P=0 = MW/RT MW = RT   Plotting:

P=0

- W(bulb

+ air)

+ Wair )]
(Berthelot

P (atm)

[1

(1-

Equation)

Kinetic Theory of Ideal Gases The Kinetic Theory is based following fundamental postulates: on the

1. Gases are considered to be composed of minute discrete particles called molecules.

For any one gas all molecules are thought to be of the same mass and size but to differ in these from gas to gas. 2. The molecules believed to be in during which they and with the walls within a container are ceaseless chaotic motion collide with each other of the container.

7. Finally, since the molecules are small compared with the distances between them, their volume may be considered to be negligible compared with the total volume of the gas. Root-Mean-Square Velocity U = Where: U = root-mean-square velocity Ux, Uy, Uz = component velocities along x, y, or z Momentum = mass x velocity (mu) Change in momentum m = m1 - m2 = mux - (-mux) = 2mux Change in Momentum per Second per Moleccule = (2mux) = 2 Total change in momentum/molecule/second = 2 + 2 + 2 = =

3. The bombardment of the contaiuner walls by the molecules gives rise to the phenomenon we call pressure (force/unit area). 4. In as much as the pressure of the gas within a container does not vary with time at any given pressure and temperature. The molecular collisions must involve no energy loss due to friction. In other words, all molecular collisions are elastic. 5. The absolute temperature is a quantity proportional to the average kinetic energy of all the molecules in a system. 6. At relative low pressures, the average distances between molecules are large compared with the molecular diameters, and hence the attractive forces between molecules, which depend on the distance of molecular separation, may be considered negligible.

= =

(U2x + U2y + U2z) U2

V/T = C' P/T = C" Charle's Law

For n' molecules in a cube V = Total change in momentum per second = V = K2T P = P = PV = Where: A cube = 6l2 F = m1 V = l
3

= = mn' =

Avogadro's Principle > equal volumes of all gases at the same pressure and temperature contain equal numbers of molecules For two gases P1V1 = P2V2 1/3 n'1m1 = m2 = 1/3 n'2m2

per mole 1/3 n'1m1 = 1/3 n'2m2

Deductions from Kinetic Theory of Gases Boyle's Law n'1 = n'2 1/2 mn'U2 = K1T n' = n x avogadros number 1/2 PV = 1/3 K1T where: PV = 2/3 K1T n = moles PV = C n' = molecular wt

N'1 = N'2 (no of molecule will be the

same) Avogadro's No (N) = 6.023x1023 mole molecules/gram-

Further Deduction from the Kinetic Theory Velocity of Gas Molecules > 1/3 nMWU2 = nRT U2 = U = =

Graham's Law of Diffusion PV = C P1V1 = P2V2 1/3 n'1m1 U21/ U22 = U1/ U2 = = = 1/3 n'2m2

Kinetic Energy of Translation Ek = = Where: ( nMu2) nRT

U1/ U2 = PV = nRT

nRT = MWU2 = 3RT On division by Avogadro's no. Ek/N = Where: K = and is degree is called the Boltzman constant equal to 1.3805 x 10-16 erg per = kT

PV = 1/3 n'mu2 = nRT PV = Where: n' = nM n' = no of molecules n = avogadro's number = nRT

Distribution of Molecular Velocities Maxwell-Boltzman Distribution Law

v = 0.921 where:

dnc/n' = 4 (

3/2

-MC2/2RT

c dc

:v:u = 1:1.128:1.224 Frequency of Collisions and Mean Free Path

dividing by dc: P = Where: P = probability of finding molecules with the velocity dnc = no of molecules out of a total n' having velocities between c and c + dc M = molecular wt T = temeperature of gas Dnc/n' = fraction of the total number of molecules having the same velocities Most Probable Velocity ( ) = Average Velocity (v) = v = 0.912u = 4 ( )3/2 e-MC2/2RT c2dc

> the number of molecules which a single gas molecule will collide per second is: v 2(n*)2 Where: v = average velocity in cm per second = molecular diameter in cm n* = n x (6.023 x 1023)

Z =

v 2(n*)2

Z = total no of colliding molecules per cc per second Nc = no of molecular collisions occurring in each cc per second Nc = = v 2(n*)2

Mean Free Path (l) > the average distance a molecule traverse before colliding l =

For diatomic gases: (H2, N2, O2 I2 Cl2) Cp - Cv = R Cv = 5/2 R Cp = 7/2 R = 1.4

For triatomic gases: (CO2, SO2, H2S N2O) = 1.3

Heat Capacity of Gases Cp = at constant pressure Cv = at constant volume Ek = RT R(T2 -T1)

Theory of Non-Ideal Gases Interaction energy (E') E' = - +

Force interaction (f') f' = where: A and B are constant molecule r = distance of separation n = constant whose value may range from 9 12 -

E = Ek2 - Ek1 = Cp - Cv = Cv = Cp = R R

H = E + PV

Specific Heat Ratio For monoatomic gases: = = = = 1.667

LIQUIDS Critical Phenomena in Liquids > properties of liquids and vapor become identical > critical points are: Critical Temperature, Tc Critical Pressure, Pc Critical Volume, Vc For H2O critical constants are:

Viscosity > resistance to flow and produce by shearing effect of moving one layer of fluid past, another and quite distinct from intermolecular attraction. Fluidity > opposite of viscosity = Where: = dynamic


viscosity

on

absolute

Tc = 374.4C Pc = 219.5 atm Kinematic Viscosity Vc = 58.7 cc per mole    Liquefaction of Gases Process involve: cooling Cooling + compressor For permanent gases: Adiabatic expansion, Q = 0 Allowing gas to cool itself by performing work in adiabatic expansion against piston. where: p = density l = mean free path l =


Viscosity of Gases = vlp

Poiseville or Stokes Equation =

1/ 2

F1 = 4/3 F2 = 6 r v

r3(p - pm)g/gc

Equating F1 and F2: = 4/3 = P = pressure t = time of flow r = radius of tube V = volume of liquid
1/ 2

r3(p - pm)g/gc = 6 r v


Where:

Fluidity ( ) = =
 

Stoke's Law > applicable to the fall of spherical bodies in all types of fluid media provided the radius of the falling body is large compared with the distance between the molecules of the fluid. Fg = F1

> the viscosity of liquid decreases with increasing temperature

W = m g/gc W = PV g/gc

FR = F2

First Law of Thermodynamics Thermodynamics = study of energy conversion Kinds of Energy > Kinematic Energy The energy a virtue of its motion > Potential Energy The energy a system virtue of its position Mechanical energy > erg (cgs) Electrical energy > joule (cgs) Thermal energy > calorie (cgs) possesses by system possesses by

A system can be: Open System > flow of energy, flow of mass (pump) > a system which can exchange both matter and energy with its surroundings Closed System > no mass flow, flow of energy (elec bulb) > one which no transfer of matter to or from the surroundings is possible, but that of energy is Isolated System > no mass flow(transfer): no energy flow > one which cannot exchanged both matter and energy with its surroundings

Thermodynamic System System > anything under study or consideration > as any portion of the universe isolated on or in an inert container, which maybe real or imaginary, for purposes of study of the effect of various variables upon the contents of the system. phase

It can be: Homogeneous System = contains only one

Heterogeneous System = two than a single phase may involved

or

more

Phase > defined as homogeneous, distinct, and mechanically portion of a system. Steady State > does not change in time True Solution > physically homogeneous mixture of two or more substances physically separable

First Law Equation: E = q - W dW = fdl = pAdl W = Wmax is attained at reversible process W = (+) work is done by the system (V2 > V1) expansion W = (-) work is done on the system (V2 < V1) compression q = (+) absorbed q = (-) evolved E = q - p(V2 - V1) a. P is constant E = q - p(V2 - V1) b. Volume is constant E = q c. free expansion P = 0; W = 0

Thermodynamics System Properties: Extensive property > dependent on the mass Intensive Property > mass independent First Law of Thermodynamics Energy can neither be created nor destroyed but it can only transform from one form to another.
PE1 + KE1 + E1 + P1V1 + Q = W + P2V2 + KE2 +E2 + P2V2

E = q

d. P is variable, T is constant W = nRT ln W = nRT ln

At constant volume: 0 C = Cv = ( =
v

Enthalpy of a System H = E + PV H = H2 - H1 = (E2 + P2V2) - (E1 + P1V1) = (E2 - E1) + (P2V2 - P1V1) = H = Where: E = internal energy If Cp = f(T) Cp = a + bT + CT + dT Cp = a + b/T + C/T
2 2 2 3

E = E = mCv T H = E

H = (E2 - E1) + (P2V2 - P1V1) H = E + Pv

E + P(V2 - V1) E + P V

H = q - P V + P V H = q H > H = E E if w = 0, w > 0 if w = 0

H = (+) absorption of heat H = (-) evolution of heat

H = n

Heat Capacity (Cp, Cv) Cp = heat capacity at constant temperature W = rate of change of the internal energy with temperature at constant volume. Cp = (
v

Difference of state of state function on variables: *E as a function of (T, V) then: E = f(T,V) *H = f(T,P) dH = CpdT + [V - T( )P]dP Thermodynamics Behavior of Ideal Gas PV = nRT For ideal gas: Cp - Cv = nR

At constant pressure: Cp = (
P

If Cp is constant: H = nCp T =

Cp - Cv = R H = H = H = E + PV Differentiating it with respect temperature at constant pressure: Cp - Cv = ( )P + P( ) - ( )v Note: = to when n = 1 when n = 1 For monoatomic gases: Cp = 5/2 R Cv = 3/2 R For diatoimic gases: Cp = 7/2 R Cv = 5/2 R

For monoatomic For diatomic For triatomic

= 1.6 = 1.4 = 1.3

Where: E = * Gas laws are not applicable in adiabatic process. Derived formula:

Isothermal and Adiabatic Process Isothermal Processes > any process conducted in a manner such that the temperature remains constant during the entire operation. E = q - w = ( 0 = q - w q = w Isothermal process in ideal gas w = W = nRT ln V2/V1 W = nRT ln P1/P2 If P is constant: W = P(V2 - V1) w = = (
    


P1V1 = P2V2 = ( )


Joule - Thompson Effect Adiabatic: E = - w E2 - E1 E2 + P2V2 H2 H

Adiabatic process in ideal gas q = 0 (no heat evolved nor absorbed) E = - w w = - E

= = = =

(P2V2 - P1V1) E1 + P1V1 H1 0

Joule - Thomson Coefficient: =( )H

  

Cp = - (  )T Cp = T ( )P - V Where:   neither = = Cp = (  )P at inversion heat or cools) (+) cooling (-) heating = 0 point (gas


> in itial and final states are equal > composed of several steps/processes

Carnot Cycle Steps > 2 isothermal (T = C) process (expansion, compression) > 2 adiabatic process (q = 0) (expansion, compression) Analysis of the cycle 1. AB --- isothermal expansion E = q2 - w1 E = 0 q2 = w1 = nRT2 lnV1/V2 = nRT lnP2/P1 w = q2 - q1 2. BC --- adiabatic expansion q = 0 E = - w2

The Carnot Cycle

A P2V2 Adiabatic Compression P

Isothermal Expansion B

P1V1

P4V4 D P3V3 Isothermal Compression V C

Adiabatic Expansion

E = 3. CD --- isothermal compression E3 = 0 E3 = -q1 - w3 q1 = -w3 = -nRT lnV4/V3 4. DA --- adiabatic compression q = 0 E4 = -w4 E4 = E cycle = 0 w max = q2 - q1

Thermodynamics Efficiency Eff = Eff = = = =

    

Calculation of H = = = = H = Where: E E E E E + + + + +

E from

H or vice versa

x 100 =

P V (PVP - PVR) (npRT -nRRT) (NP -NR) RT ngRT

x 100 x 100 ng = nP - nR

ThermoChemistry > branch of physical chemistry which deals with the thermal changes accompanying chemical and physical transformation. Heat lost = heat gained qH = mCp T Heat of Pressure ReaCTION AT Constant Volume or

Hess' Law of Heat Summation > the heat of reaction must be independent of the particular manner in which the reaction takes place Heat of Combustion > for combustible material > amount of heat liberated substance burned Hrxn = 

per

mole

of

E = q - w q = E + V = 0

Heat of Formation > heat involved in the formation of 1 mole of substance from the element. Kirchhoff's Equation Cp = CpP - CpR Cp = [ E2 =
 

at constant volume: q = E at constant pressure: q = H where: H + H +

]P 

E = (+) heat is absorbed E = (-) heat is evolved

The Second and Third Law of Thermodynamics > The flow of heat is unidirectional, always from higher temperature region to lower temperature region. > All naturally occurring process always tend to change spontaneous in a direction which will land to equilibrium. > Heat cannot be converted to work which leaving permanent changes either in systems involved or in their surroundings. Haber Process q2 = q1 + W T2

At constant temperature: = S = Entropy Change in Isolated Systems Reversible expansion: Ss = Sr = V1 - V2

System

=


Ss + +

Sr

System

= = 0

q2 W Isolated System Under Non-Isothermal Condition Founds: > for any reversible process or cycle S = 0 > for any irreversible process or cycle S = ; S > 0

Entropy

q1

> degree of disorder > state of a function > depends only on initial and final state of the system S = S2 - S1 dS = where dq = infinite quantity of heat

The Second Law of Thermodynamics > All process in nature tend to occur only with an increase in entropy and that the directions of change is always such as to the entropy increase. dsi > 0

Entropy Change for Systems Only ds = ds + dsr > 0 system + reservoir dsr = ds + dsr ds Tds - dq


In Isolated System S = nRln S = nRln S = -nRln Dependence on Temperature and Volume

> 0 > 0 > 0

E = q - w dE = dq - dw dq = dE + dw > 0 ds = ( )v dT + ( )T dV = dT + )vdV + nR ln

Tds - dE - pdV -dw'

S = nCv ln S = f (T,P) S = ncP ln

For irreversible process Tds - dE - PdV - dw' > 0 PV = nRT P = P1 dw' = dw'm Tds - dE - PdV - dw;mx = 0 Tds - dE - PdV = 0 Entropy Change in Ideal Gases Isothermal dE = 0 Tds = PdV ds = ds = =

+ nR ln

Entropy of Mixing for Ideal Gas Sm = n1R ln Sm = n1R ln If = + n2R ln + n2R ln

= PT (special cases)

Sm = - (n1RlnN1 + n2RlnN2)

Entropy Change in Physical Transformations S = S2 - S1 S = where: = Hs

Free Energy and Equilibrium > capability of the rxn to do work Helholtz Free Energy (A) A = E - TS At constant temperature: A = A2 -A1 = (E2 -TS2) - (E1 - TS1) = E - T(S2 - S1) A = E - T( S) If T is not constant: A = (E2 -TS2) - (E1 - TS1) = E - (T2S2 - T1S1) A = E - TS S =

Hv = latent heat q = Hv = Hf = Hs = Hv + Hf S = S = S = S =
  

L - G G - L S - L S - G

(evaporation) (cooling) (melting) =

 

(sublimation)

q = sensible heat q = mCp T Change Entropy in Chemical Reactions A + bB + = cC + dD + S = S = S2 = ; = if cP is constant

qr = T S At constant temperature: A = E - T S = E - qr = - w Wmax = - A Where: in first law of thermodynamics E = q - w E - q = - w At constant temperature; ideal gas W = nRT ln


S1 + nCpln

Third Law of Thermodynamics ST = ST =

= nRT ln

A for Reactions A = E - TS dA = dE - (TdS + SdT) A = f (T,V) a) dA = ( )vdT + ( )dV b) dA = dE = dE Where: dqr = dE + dqr = dE + - TdS - SdT - SdT - dqr dw pfV

The Gibbs Free Energy (G) G = H - TS G = G2 -G1 G = H - T S G = H - qr = E + PV - qr = E - qr + PV = A + PV G = A + PV G = - (Wm - P V) Where: A = f (T,V) G = f (T,P) G1 = (H1 - T1S1) = G2 G = A + PV S = A = - w E = q - w E - q = A G = f (T, P) dG = VdP - SdT

if T is constant

dA = dE - SdT - (dE + pdV) dA = - SdT - pdV Where: -S = ( )v -P = ( )T Therefore: ( )v = =

      

A = E - TS

( )v = ( )v = Where: E = f(T) E = ( )v = dT  dT

]P = = = ( ) =

Where: -S = ( )P V = ( )T G = H - TS H = G + TS ( )P = ( ) =


Fugacity and Activity Concepts G = RT lnf + B At standard state: G0 = RTlnf0 + B G = G0 + nRT ln f/f0 G = G0 + 1 G = G0 Per Mole: G = nRT ln Where: f/f0 = a a = 1 Standard State for Gases Where: f0 = 1 f = P a = f/f G H (absorbed) (evolved) a = f G = G0 + RT lnf
0

Properties and Significance of G AT constant T, P: G = 0 @ equilibrium G = spontaneous G = + non - spontaneous G G qr qr qr = H = H = H (+) = (-) = T S qr G H > G >

as P = 0 = 1

lim P-0

Calculations of Free Energy Changes At constant temperature: G = V P if V is constant If V = f (T) ; ideal gas G = nRT ln G = nRT ln

(activity coefficient) ideal gas

Determination of Activity Coefficients of Gases dG = VdP ; G = V P G = G0 + RT lnf

dG = RTdlnf dlnf =

The Reaction Isotherm A + bB cC + dD + RT ln aA + RT ln aB + RT ln aC + RT ln aD

dlnf = = ( = + + ) GA = GB = GC = GD =

= dlnP + Dlnf - dlnP = Where: = V V = = dln = dln = lny lny = = (P - 0) if T and is constant If: Standard States for Solid and Liquids > As the standard of pure solid or liquid is taken the solid or liquid at 1 atm pressure at each temperatue. a = 1 = +

Grxn = = (cGC + dGP) - ( GA + bGB) G = G0 + RT ln (ln / )

Criteria of Equilibrium Where: G = 0 H = E + PV G = H - T S TdS = dE - PdV = 0

V = C ; E = C dV = 0 ; dE = 0 Then: TdS - 0 - 0 = 0 TdS = 0 dS = 0 ( S)E,V = 0 at equilibrium

If: T and V are constants dA + 0 + 0 = 0 (dA)T,V = 0 ( A)T,V = 0 Then: A = E - TS dA = dE - TdS - SdT TdS - dE = -dA - SdT -dA - SdT -PdV = 0 dA - SdT - PdV = 0 3 Criteria of ( S)E,V = ( G)T,P = ( A)T,V = AT constant dG + 0 (dG)T,P ( G)T,P Then: G = H - TS = E + PV - TS G = A + PV dG = dA + PdV + VdP dA + PdV = dG - VdP -SdT = dG - VdP dG + SdT - VdP = 0 where: A = E - TS T = = Equilibrium 0 0 0 and P: 0 = 0 0 0

Physical Substances

equilibrium

Involving

Pure

At equilibrium: dG = 0 dT = dP = 0 G = 0 G2 - G1 = 0 G2 = G1 dG = -SdT + VdP -S2dT + V2dP (V2 - V1)dP dP/dT = Where: S = q/T ; q = S = H/T Therefore: = H = = = = dG1 = -S1dT (S2 (S2 -

dA A A2 A2

= = =

0 0 A1 = 0 A1

dG2 + V1dP S1)dT S1)/(V2 - V1)

--- clayperon equation

Uses of Clayperon Equation

 

 

= ( ) =

P2 - P1 =

ln

The Boiling Point of Liquids Liquid to Vapor (Evaporation/Condensation) H = = = Where: V V PV Vg = = = = Vg - VL Vg nRT nRT/P Hv

Sublimation (Solid to Gas) Hs = Hv + Hf V = Vg - Vs = = By substitution and integration: ln = (



By substitution: integration: ln = (

 

where: Vg >>> Vs V = Vg PV = nRT V = nRT/P

Solid to Liquid (Fusion) H = Hf where: = By substitution: integration: P2 - P1 = Troutons Rule = c = 21 ln

V = Vl - Vs

Physical Chemistry I
Physical Principles

Alfredo Samsona Jr.