(Chap.

5, 19)

Thermodynamics:
Enthalpy, Entropy & Gibbs Free Energy
S +
G = negative
spontaneous at all temperatures

G = ??
spontaneous at high temperatures

+
G = positive
non-spontaneous at all temperatures

G = ??
spontaneous at low temperatures

Thermo 2

Thermodynamics:

thermo = heat (energy) dynamics = movement, motion

Some thermodynamic terms we'll be using: System: the portion of the universe that we are considering open system: energy & matter can transfer closed system: energy transfers only isolated system: no transfers Surroundings: everything else besides the system Isothermal: a system that is kept at a constant temperature by adding or subtracting heat from the surroundings. Heat Capacity: the amount of heat energy required to raise the temperature of a certain amount of material by 1C (or 1K). Specific Heat Capacity: 1 g by 1C Molar Heat Capacity: 1 mole by 1C

Thermo 3

Calorie: the amount of heat required to raise the temperature of 1g of water by 1C. specific heat of water = 1 cal/g C

1 calorie = 4.18 joules

Specific Heats and Molar Heat Capacities
Substance Al Cu Fe Ethanol Water Specific Heat (J/Cg) 0.90 0.38 0.45 2.43 4.18 Molar Heat (J/Cmol) 24.3 24.4 25.1 112.0 75.3

EXAMPLE: How many joules of energy are needed to raise the temperature of an iron nail (7.0 g) from 25C to 125C? The specific heat of iron is 0.45 J/Cg. q = Heat energy = (specific heat)(mass)(T) Heat energy = (0.45 J/Cg)(7.0 g)(125-25C) = + 315 J

*The sign (+/-) is very important as you will see. + heat absorbed- endo - heat released- exo

Thermo 4

Energy: "The capacity to do work and/or transfer heat" E=q+w Forms of Energy:
Kinetic (Ekinetic = mv2) Potential Heat (Electromagnetic) Light (Electromagnetic) Electricity Chemical Nuclear Matter (E = mc2)

WORK

Thermo 5

First Law of Thermodynamics: The total amount of energy (and mass) in the universe is constant. In any process energy can be changed from one form to another; but, it can never be created nor destroyed.

"You can't get something for nothing"

Relationship btw heat (q) & work Where q = + heat is added Where q = - heat is lost Work is movement of something over distance, w = - PdV If distance increases (+) then w = If distance decreases (-) then w = + Filling a hot air balloon q = + & w = Letting hot air balloon cool down/deflate q=-&w=+

Thermo 6

Enthalpy (Heats) of Reaction

The amount of heat released or absorbed by a chemical reaction at constant pressure (as one would do in a laboratory) is called the enthalpy or heat or reaction. We use the symbol H to indicate enthalpy. H = q/mol Sign notation (EXTREMELY IMPORTANT!!):

+H indicates that heat is being absorbed in the

reaction (it gets cold) endothermic indicates that heat is being given off in the H reaction (it gets hot) exothermic Standard Enthalpy = H ( is called a "not")

Occurring under Standard Conditions: Pressure 1 atm (760 torr) Concentration 1.0 M Temperature is not defined or part of Standard Conditions, but is often measured at 298 K (25C). H *mol = q at constant pressure (kJ)

Standard Enthalpy of Formation :

H f

Thermo 7

The amount of heat absorbed (endothermic) or released (exothermic) in a reaction in which one mole of a substance is formed from its elements in their standard states, usually at 298 K (25C). Also called heat of formation.

H = 0 for any element in its standard state (the f

natural elemental form at 1 atm or 1 M). EXAMPLES: A Formation Reaction
C(graphite, s) + O (g) 2 H = 0 kJ/mol rxn 0 kJ/mol CO2 (g) 393.5 kJ/mol

elements in their standard states

negative sign heat released -- exothermic rxn

product (one mole)

H (CO2 ) = f

393.5 kJ/mol

Thermo 8

2H2 (g) + O2 (g) H = 0 kJ/mol rxn 0 kJ/mol

2H2 O (g) 483.6 kJ/ 2 mol

elements in their standard states

negative sign heat released -- exothermic rxn

product (two moles)

divide by 2 to put on per mole basis!!

H (H2 O) = f

241.8 kJ/mol

Stoichiometry of Thermochemical Equations

A thermochemical equation is a balanced equation that includes the heat of a reaction (HRXN). Keep in mind that the HRXN value shown refers to the amounts (moles) of substances in the balanced chemical reaction. For example:
SO2 (g) + O2 (g) SO3 (g) where, HRXN = - 99.1 kJ/mol

STRATEGY:

Thermo 9

1.

Calculations are based on the number of moles of a given substance (grams MM = moles) and the other stuff is assumed to be in Excess or ignored. That is to say, the amount of whatever affects the magnitude of HRXN. Once moles of a given substance is known, then we use the given HRXN value (kJ/mol) to calculate the overall HRXN in kJ. Where the Stoich. Coef comes into the calculations is here for the substance of interest only! Strategy Summary:

2.

kJ

mol

(of given substance)

Grams x

1 MM

kJ

= = kJ of Reaction!

(of given substance)

mol
(of given substance)

Example (1): 2 CO (g) + O2 (g) 2 CO2 HRXN = - 482 kJ/mol If we react 12.0 g of CO, whats HRXN (kJ)? 12.0g x 1 mol of CO x 2 - 482of CO = - 103.3 kJ ! mol kJ 28.0 g

Thermo 10

Example (2): 2 Al (s) + 3 O2 (g) 2 Al2O3 (s) HRXN = - 3351 kJ/mol If we produce 75.0 g of Al2O3, whats HRXN (kJ)? 75.0g x 1 mol of Al2O3 x - 3351 kJ 102.0 g 2 mol of Al2O3 = -1232 kJ !

A sample of CH6N2 (l) underwent combustion. Calculate the mass of CH6N2 (l) (MM = 46 g/mol) that reacted if 1877 kJ of heat are released. 2 CH6N2 (l) + 5 O2 2 N2 (g) + 2 CO2 (g) + 6 H2O (l)

H = -1300 kJ/mol

Thermo 11

Hess's Law & Adding Reactions Hess Law: The overall heat of reaction (Hrxn) is equal to the sum of the Hf (products) minus the sum of the Hf (reactants):

I.

Therefore, by knowing Hf of the reactants and products, we can determine the Hrxn for any reaction that involves these reactants and products. Adding Reactions Also, one can add two or three reactions (and their given Hrxn) together to get the Hrxn for another new reaction
II.

H r x n= [ #m o] [l H f ( p r o d u ct s[ #m o] [l H f ( r e a c t) a] n t s ] )

Thermo 12

4.

When you add the 2 or 3 reactions together, they must give you the overall Hrxn for the reaction sought for. 2. Compare the position of reactant & products and quantity. Dont worry about what is suppose to cancel out. It will! 3. If you multiply the reaction by a coef (number or fraction), you must multiply that times the Hrxn for that reaction. If you must flip the reaction around. You must change the sign on the Hrxn for that reaction.
1.

Thermo 13

EXAMPLE: CO2 is used in certain kinds of fire

extinguishers to put out simple fires. It works by smothering the fire with "heavier" CO2 that replaces oxygen needed to maintain a fire. CO2 is not good, however, for more exotic electrical and chemical fires.
2Mg(s) + CO (g) 2 2MgO(s) - 602 kJ/mol + C(s) - 393 kJ/mol 0 kJ/mol

H = 0 kJ/mol f

REACTANTS

PRODUCTS

H = rxn H = rxn

(# mol) H (products) (# mol) H (reactants)

f f

(2 mol)(-602 kJ/mol) + (1 mol)(0 kJ/mol) (2 mol)(0 kJ/mol) + (1 mol)(-393 kJ/mol)

(-393 kJ)

H = (-1204 kJ) rxn

H = (-1204 kJ) + 393 kJ rxn H = rxn 811 kJ

highly exothermic rxn !!

Therefore, Mg will "burn" CO2 !

Thermo 14

Calculate H rxn

for the following reaction: C 2 H5 OH(l) H = ?? rxn

C2 H4 (g) + H O(l) 2

Given these two reactions and thermodynamic data: a) C 2 H5 OH(l) + 3O (g) 2 b) C2 H4 (g) + 3O (g) 2 2CO2 (g) + 3H O(l) H = -1367 kJ/mol 2 rxn 2CO2 (g) + 2H O(l) H = -1411 kJ/mol 2 rxn

How to solve: 1) C 2 H5 OH is on the productside of the first reaction -- so we want to switch equation a) around to get2 H5 OH also on the C productside: 2CO2 (g) + 3H O(l) 2 C 2 H5 OH(l) + 3O (g) H = +1367 kJ/mol 2 rxn

2) Now we can add the two reactions together to give us the desired net reaction: 1 2CO2 (g) + 3H O(l) C 2 H5 OH(l) + 3O (g) H = +1367 kJ/mol 2 2 rxn

note that when we reverse the reaction, Hrxn changes sign!!!

C2 H4 (g) + 3O (g) 2 C2 H4 (g) + H O(l) 2

2CO2 (g) + 2H O(l) H = -1411 kJ/mol 2 rxn C 2 H5 OH(l) H = -44 kJ/mol rxn

If we have to multiply one (or more) of the reactions by some constant to get them to add correctly, then we also would have to multiply Hrxn for that reaction by the same number.

Thermo 15

The measurement of heat flow is called calorimetry. Chemists use bomb calorimeters to measure Enthalpies of formation or reaction. Uses
q = Heat energy = (specific heat)(mass)(T)

B
S

o m
t i r
E l e c o t o r e s ra c o m

a l o r i m
l e

e t

c t r i c a l n t a c t s i n i t a tT e h e r m o c o u p m e a s u r e m p l et o t t e i om n p e r a t u r e b u s

S a m p l e p l a c e d i n s i d e i n n e r c o n t a i n e r

W
H i g h l y i n s u l a t e d

a t e r
o u t s i d e c o n t a i n e r

T h i c k - w a l l e d i ( b o m b ) t o c o n o f s a m p l e ( p r e

n n e r c o n t a i n e r t a i n c o m b u s t i o n w i t h O 2s s u r i z e d

In order to use this effectively one must know the heat capacity of the bomb (inner part) and water bath. By measuring the temperature increase of the water one can calculate the amount of heat given off during the combustion process.

Thermo 16

Problem: Consider some substance 5 grams AB (molar mass = 40 g/mol) dissolves in 50 grams of water at constant pressure. The specific heat of solution (water) is 4.18 J/gC and Hsoln = +10 kJ/mol. Assume no heat transfers. What is the change in temperature?

Thermo 17

Sample Problem: Calculate Hrxn for the following reactions given the following H values: f
H (SO2, g) = 297 kJ/mol f H (H2SO4, l) = 814 kJ/mol f H (H2O, l) = 286 kJ/mol f H (SO3, g) = 396 kJ/mol f H (H2SO4, aq) = 908 kJ/mol f H (H2S, g) = 20 kJ/mol f

a) S(s) + O2(g)

SO2(g)

b) 2SO2(g) + O2(g)

2SO3(g)

c) SO3(g) + H2O(l)

H2SO4(l)

Thermo 18

Thermo 19

Entropy
As you add heat to a material you are increasing the disorder of that system. The thermodynamic term that measures the disorder of a system is called entropy. We use the symbol S to indicate entropy.
Ice - well ordered structure water vapor - most disordered

water - more disordered

Unlike H, entropy can be defined exactly because of the Third Law of Thermodynamics:

Third Law of Thermodynamics: Any pure crystalline substance at a temperature of absolute zero (0.0 K) has an entropy of zero (S = 0.0 J/K mol).

Thermo 20

Sign notation (EXTREMELY IMPORTANT!!):

+S indicates that entropy is increasing in the

reaction or transformation (it's getting more disordered -- mother nature likes) S indicates that entropy is decreasing in the reaction or transformation (it's getting less disordered {more ordered} -- mother nature doesn't like, but it does happen) Qualitative "Rules" About Entropy: 1) The Entropy of any material increases with increasing temperature 2) Entropy increases as one goes from a solid to a liquid, or more dramatically, a liquid to a gas.
250 Solid 200 Liquid Gas

150 phase transitions

100

50

100

200

300

Thermo 21

3) Entropy increases if a solid or liquid is dissolved in a solvent. 4) Entropy increases as the number of particles in a system increases N2O4(g)
S = 304 J/K(1 mole)

2NO2(g)
S = 480 J/K (2 moles)

5) Entropy increases as the mass of a molecule increases S(Cl2(g)) > S(F2(g))

S = 165 J/Kmol S = 158 J/Kmol

6) Entropy is higher for weakly bonded compounds than for compounds with very strong covalent bonds S(graphite) > S(diamond)
S = 5.7 J/Kmol S = 2.4 J/Kmol

Thermo 22

7) Entropy increases as the complexity (# of atoms, # of heavier atoms, etc.) of a molecule increases
Entropy of a Series of Gaseous Hydrocarbons
H H C H H Methane

S = 186 J/Kmol
H

Acetylene

S = 201 J/Kmol S = 220 J/Kmol S = 230 J/Kmol

H C H
H H C H
H H C H

H C H
H C H
H C H H C H H Propane

E th y le n e

H Ethane

S = 270 J/Kmol

What are the biggest factors for evaluating Srxn for a chemical rxn? 1) phase change 2) change in # of molecules Interpreting the entropy of a reaction ( or ):

Thermo 23

1.

Is there a gas phase present on one side? Mg(s) + 2 HCl (aq) MgCl2 (aq) + H2 (g) S = + (increasing) The further apart the molecules the more disordered the system. MgCl2 (aq) + H2 (g) Mg(s) + 2 HCl (aq) S = - (decreasing) Bringing them closer together more ordered.

2.

Gas phases on both sides look at number of particles. 2NO2(g) N2O4(g) S = - (decreasing) Bringing them closer together more ordered. Or phase changes. H2S(g) + O2(g) H2O(l) + SO(g) S = - (decreasing) gas to liquid - bringing them closer together more ordered.

Thermo 24

Sample Problem: For the following reactions, is the entropy of the reaction increasing or decreasing? a) Ag+(aq) + Cl-(aq) b) H2CO3(aq) c) Ni(s) + 4CO(g) d) H2O(s) e) 2Na(s) + 2H2O f) H2S(g) + O2(g) g) 2H2O(l) h) CO2(g) + CaO(s) i) CaCl2(s) + 6H2O(l) j) 2NO2(g) N2O4(g) H2O(l)
2Na+(aq) + 2OH-(aq) + H2(g)

AgCl(s) H2O(l) + CO2(g) Ni(CO)4(l)

H2O(l) + SO(g) 2H2(g) + O2(g) CaCO3(s) CaCl26H2O(s)

Thermo 25

Just as with enthalpies, one can calculate entropies of reaction. EXAMPLE:

2Mg(s)

Sr x n = [# m o][S (p ro d u c ts [#m o][S (re a c ta n]ts l )] l )

+ CO2 (g) 2MgO(s) 27 J/Kmol + C(s) 6 J/Kmol

Srxn = 32 J/Kmol 215 J/Kmol Sf

REACTANTS

PRODUCTS

S = rxn S = rxn

(# mol) S (products) (# mol) S (reactants)

f f

(2 mol)(27 J/Kmol) + (1 mol)(6 J/Kmol) (2 mol)(32 J/Kmol) + (1 mol)( 215 J/Kmol)

(279 J/K) 219 J/K

S = (60 J/K) rxn S = rxn

entropy is decreasing (reaction is becoming more ordered)

Thermo 26

Boltzman-Molecular Interpretation of Entropy As chemist, we are interested in molecules... What does Enropy have to do with them and their transformations? What molecular property does Entropy reflect? To develop this we need to understand how molecules respond to Energy. We know from 1201, that when a substance is heated, the motion of the molecules increases, rms velocity, u. Which is directly proportional to temperature: The most probable speed of a gas molecule is the peak of the Boltzman distribution:

u=

3RT
(MM)

Average kinetic energy of a gas, , is determined by this equation, = mu2

Thermo 27

Well what types of Motion are there? Glad you asked Molecules undergoe three kinds of motion: Translational motion- the molecule moves in one direction. Vibrational motion- where atoms in a molecule are moving towards and away from one another. Rotaional motion- is a spinning of the molecule. These different forms of motion are ways in which molecules can store energy. Lets consider one mole of an ideal gas ~6 x 1023 molecules, in a thermodynamic state, some P, V, T amount. What happens to this collection when we change the temperature? Now imagine that we could take a snap shot of the positions (motions) and speeds at an instant in time. That set of 6 x 1023 positions (motions) and enegies of the individual gas molecules is called a microstate. As we continue to take snapshots of our collection we could see all the other possible microstates. Since we are examining a large collection of

Thermo 28

molecules, there is an average possible arrangement of these molecules within these microstates, which is defined by statistcs. Therefore, each thermodynamic state (ie. defined by a certain P, V & T) has a certain number of microstates associated with it, we designate by the symbol W. The connection between the number of microstates of a system, W, and its enropy is expessed by the simple Boltzman equation:

S= klnW
Where, k, the Boltzmans constant, 1.38 x 10-23 J/K. Thus the Entropy is a measure of number of different microstates associated with a collection of molecules. Therefore, the more complex the molecule, the greater the number of microstates, the higher the entropy. System, Surroundings, and Universe Look at this figure of ice melting in someones hand. Heat is required to melt the ice. This heat must come from the surroundings (the hand + everything else).

Thermo 29

qsys = + (Endo)
ICE Syste m

+HEA T

Surroundings

qSurr = -

Surroundings

We can see that: SSys =+ or 0< because the s l phase change increases the disorder of the system, heat is being absorbed, qsys = + (Endo) SSurr = - or 0> because heat is leaving the surroundings, qSurr = - . The temperature of the surroundings is dropping (cold to the touch) and the surroundings is becoming more ordered. SUniv =+because we know the process to be spontaneous at this temperature, but it is temperature dependent of course - More about this see Gibbs Free Energy Conversley, Look at this figure of water forming Ice in a freezer. Heat loss is required to freeze the water. This heat must come from the system (water) and absorbed/pulled out by the surroundings- the freezer.

Thermo 30

qsys = - (Exo)
HEAT

ter wa

ICE Syste m

Surroundings

qSurr = +

Surroundings
(absorbing heat)

We can see that: SSys = - because the l s phase change and the system is becoming ordered, heat is being lost, qsys = - (Exo) SSurr = + because heat is entering the surroundings, qSurr = + . The temperature of the surroundings is increasing (and the freezer has to do something about that-another story); therefore the surroundings is becoming more disordered. Finding Entropy This figure is a summary of the way to find the changes in entropy. All of these quantities can be calculated but that requires a more advanced course. An example of how to use this procedure is shown above.

Thermo 31

1. Ssys is deduced by looking at the process in the system to see if the system is becoming more ordered or more disordered. a. Ssys = + or Ssys >0 increase in disorder b. Ssys = or Ssys <0becoming ordered 2. Ssurr is determined from the heat flow. a. If heat enters the surroundings, they heat up, disorder increases, Ssurr = + b. If heat leaves the surroundings, they cool down, order increases, Ssurr = 3. Suniv is determined from whether the process is spontaneous, non-spontaneous - See Gibbs Free Energy -Next a. Suniv > 0 Reaction is spontaneous b. Suniv < 0 Reaction is non-spontaneous

Thermo 32

Examples: Indentify, + or -, or >0 or <0, for the following terms given certain conditions: 1. Sublimation of Iodine, I2 (s) I2 (g) qSys = qSurr = SSys = SSurr = Condensation of water, H2O (g) H2O (l)

2.

qSys = qSurr = SSys = SSurr =

Spontaneous Processes
A process that takes place without the net input of energy from an external source is said to be spontaneous. 1) Rxn of sodium metal with water:
2Na(s) + 2H2O 2Na+(aq) + 2OH-(aq) + H2(g)

Thermo 33

2) Combustion rxns: 2C2H6(g) + 7O2(g) 4CO2(g) + 6H2O(g) 2H2(g) + O2(g) 2H2O(l) 3) Expansion of a gas into a vacuum xCO2(g) yCO2(s) + zCO2(g)

4) A salt dissolving into solution:

NH4NO3(s) + H2O(l) NH4+(aq) + NO3-(aq)

Thermo 34

Second Law of Thermodynamics: In any spontaneous process the entropy of the universe increases
Suniverse = Ssystem + Ssurroundings

Second Law (variant): in trying to do work, you always lose energy to the surroundings.

You can't even break even!

Neither entropy (S) or enthalpy (H) alone can tell us whether a chemical reaction will be spontaneous or not. An obvious (?) conclusion is that one needs to use some combination of the two.

Thermo 35

Gibbs Free Energy The combination of entropy, temperature and enthalpy explains whether a reaction is going to be spontaneous or not. The symbol G is used to define the Free Energy of a system. Since this was discovered by J. Willard Gibbs it is also called the Gibbs Free Energy. "Free" energy refers to the amount of energy available to do work once you have paid your price to entropy. Note that this is not given simply by H, the heat energy released in a reaction.

G = H TS
When G is negative, it indicates that a reaction or process is spontaneous. A positive G indicates a non-spontaneous reaction.

Thermo 36

G = H TS
S +
G = negative
spontaneous at all temperatures

G = ??
spontaneous at high temperatures

+
G = positive
non-spontaneous at all temperatures

G = ??
spontaneous at low temperatures

Thermo 37

Remember that entropies are given in units of J/Kmol while enthalpies and free energies are in kJ/mol. DON'T forget to convert all units to kJ or J when using both S and H in the same equation!!
DANGER!! Common mistake!!

Example: Calculate Grxn for CO2 at 298 K. Hf (CO2) = -393 KJ/mol, S (O2) = 205 J/molK, S (C) = 6 J/molK, S (CO2) = 213 J/molK C(graphite) + O2(g) Grxn= Hrxn TSrxn Srxn = CO2(g)
Note change in units J to KJ

Thermo 38

Sprod Sreact Srxn = (213 J/molK) (205 + 6 J/molK) Srxn = 2 J/molK) Hrxn = Hf (CO2)

Grxn = (393 kJ/mol) (298 K)(0.002 kJ/molK) Grxn = (393 kJ/mol) (0.6kJ/mol) Grxn = 393.6 kJ/mol DANGER!! Common mistake!!

Thermo 39

Just as with enthalpies and entropies, one can calculate free energies of reaction. EXAMPLE:
2 M G f g

G = [# mol ][ G (products )] [# mol ][ G (reactants ) ] rxn

( s )
2

C k J / m-

O2 M

( g g O)

( s )

+ o l

0 = k J / m - o3 l 9 4

o 7l 0 5

k J 0 / m k o /l m J

T A

G r G r

x x x n n n

(= #

m G f l ) ( p o m o

r o

u ( c#
o

t s ) G f l ) ( r e a c t a m o o l ) + o ( 1 l ) m + o (

(= 2

l ) ( - 5 7 0

k J / m l ) ( 0

( - =1 1 4 0

( 2

k J / m

G r G r G r C T o m

k( - J3 ) 9 4

k J ) k J

( - =1 1 4 0 + k3 J )4 9 7= 4 6

S P O k hJ i g h w 6 5

N T A l y e x a s

N E o t h - 8 1 1

U e r m k J e P r Yg

S r x n i c r x f o y w r t

p H rr ex w t oh i c h a n "i s s i n g "

h m e

k EJ N o T f R e O n

e n

Thermo 40

Example: To make iron, a steel mill takes Fe2O3 (rust or iron ore) and reacts it with coke (a complex, impure form of carbon) to make iron and CO2. Based on the data below, this is a non-spontaneous reaction at room temperature, but it becomes spontaneous at higher temperatures. Assuming that H and S do not change much with temperature, calculate the temperature above which the reaction becomes spontaneous (i.e., Grxn = 0).
Hrxn = +465 kJ/mol Srxn = +552 J/molK (or 0.552 kJ/molK) Grxn = +301 kJ/mol (at 298 K)

Grxn = Hrxn TSrxn

as we raise the temperature, G will eventually reach 0 and then go negative & spontaneous, so let G = 0 and solve for T, the temperature at which this will happen:

0 = Hrxn TSrxn
rearranging to solve for T gives:

T = (Hrxn) / (Srxn) T = (465 kJ/mol) / (0.552 kJ/molK) T = 842 K

(above this temperature Grxn will be negative we will have a spontaneous reaction)

Thermo 41

Entropy of Fusion and Vaporization

While the entropy of a substance increases steadily with increasing temperature, there is a considerable jump in the entropy at a phase transition:
250 Solid 200 Liquid Gas

150 phase transitions

100

50

100

200

300

At the phase transition, we are at equilibrium with two phases and G = 0. This jump at the melting point is called the entropy of fusion, Sfusion, and as you might expect, it is related to the enthalpy (or heat) of fusion, Hfusion:

Hfusion S fusion = Tm

Thermo 42

The jump in entropy at the boiling point is called the entropy of vaporization, Svaporization, and it is related to the enthalpy of vaporization, Hvaporization:

Hvaporization S vaporization= Tb
Br2(l)
= S H Tb

EXAMPLE: What is the boiling point of bromine (Br2)? S = 93.2 J/Kmol and H = 30.9 kJ/Kmol.
Br2(g)

but we want to solve for Tb, the boiling point temperature, so we need to rearrange the formula:
H S 3 .9 0 3 J / m 0 1 ol Tb = 93 .2 J / K m l o Tb =3 .5 K =58 .3 31 C Tb =

Note how to G & the Equilibrium Constantwe haveJ/mol in convert kJ/mol to

As Ive mentioned during the first part of this chapter, the equilibrium constant is directly related to the Gibbs Free Energy, G. G = negative Kc > 1 (spontaneous)

order for the units on H to be the same as the units on S!! To convert kJ to J we need to multiply the kJ value by 1000.

 G = zero G = positive

Thermo 43

Kc = 1 Kc < 1 (non-spontaneous)

The mathematical relationship for calculating G, given Kc is:

R = 8.314 J/K (gas constant)

G = R T l n K ( c or a or b)

T = Temp in K

Given the value of G, we can rearrange the above equation to solve for Kc: Kc = e( G/RT) Thus, given G (or H and S) we can calculate Kc at a given temperature. Similarly, given Kc, we can calculate G. Example: A reaction has a G value of 40 KJ/mol at 25C. What is the Kc for this reaction? First convert the temperature from C to K: Temp (K) = 25C + 273 = 298 K Now we can use the formula for calculating Kc:
Dont forget to carry along the sign on G

Kc = e(G / RT)

Thermo 44

Kc = e((40000 J/mol) / (8.314 J/mol K)(298K))

Important Note: R the gas constant has units of J/molK, while we usually express G in KJ/mol. The units must match!!! The easiest thing is to multiply the G value in KJ/mol by 1000 to give J/mol.

DANGER!! Common mistake!!

Kc = e (16.14) Kc = 1.02 x 107 The negative G represents a spontaneous reaction. See how this converts over to a large positive Kc value, indicating that the reaction goes mainly to products. Note also how there are no units when you calculate Kc this way.

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Example: A reaction has a Kcvalue of 0.01 at 25C. What is G for this reaction? First convert the temperature from C to K: Temp (K) = 25 + 273 = 298 K Now we can use the formula for calculating G: G = R T l n K c G = (8.314 J/molK)(298K) ln(0.01) G = (2477 J/mol)(4.6) G = +11,394 J/mol -- or -- +11.4 KJ/mol Dont forget to convert J/mol to KJ/mol for the G value!! DANGER!! Common mistake!!

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Problem: A reaction has a Kc value of 10 at 25C. What is G for this reaction?

G vs. G: Standard vs. Non-Standard Conditions

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Remember that the (not) on G indicates that the numerical value of G is based on the reaction at standard conditions (1 M solution concentration, 1 atm gas pressure). Temperature is NOT part of standard conditions! As soon as one has a concentration different than 1 M or 1 atm pressure, the not goes away and one has G. Consider the reaction:

Initial:

1M 1 M 1 M [ Q = 1] 2SO2(g) + O2(g) 2SO3(g)

Grxn = 150 kJ/mol, but Q K (Re: K = e-G/RT where Keq = 1.96 x 1026 at 298K ie Q<<K )
The Grxn of 150kJ/mol is for when each gas is present with a concentration of 1 M. This indicates that the reaction under these conditions will proceed to make products (spontaneous). As the reactants start reacting, however, their concentrations decrease (SO2 twice as fast as O2) and G turns into G and becomes less negative. When G = 0 the reaction has reached equilibrium.

G: Gibbs Free Energy under nonstandard conditions; not at equilibrium. The energy to

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reach equilibrium plus free energy of the reaction. where: G = G + RT lnQ

G is Gibbs free energy under std conditions R is a gas constant 0.008314 kJ/molK T is temp. in degrees Kelvin Q is the old reaction quotient from equilibrium Recall components in liquid or solid phase have a value of 1. **At Equilbrium Q = K and G= - RT lnK

Example:What is the value of G at 400 K, if at some nonequilibrium time, the concentrations of [H2] is 0.5M, [O2] is 1.0 M and [H2O] is 2.0M and Grxn = - 228 kJ/mol. R = 0.008314 kJ/molK

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2H2(g) + O2(g) G = G + RT lnQ

2H2O(g)

G = - 228 kJ/mol + (0.008314)(400 K) lnQ lnQ = ln[(H2O)2/(H2)2(O2)] lnQ = ln[(2.0)2/(0.5)2(1.0)] = ln(16) = 2.772 G = - 228 kJ/mol + (0.008314)(400 K)(2.772) G = - 228 kJ/mol + (9.218kJ/mol) = G = 218.78 kJ/mol

As tough as it gets: Consider the following reaction mixture in a closed container at 298 K: 1.0 atm N2, 3.5 atm H2, 0.25 atm NH3 (R = 0.008314 kJ/mol-K). Is the reaction at equilibrium and what is the Grxn? N2 (g) + 3 H2 (g) 2 NH3 (g)

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Hf (kJ/mol) S (J/mol) N2 (g) H2 (g) NH3 (g) -46.19 191.5 130.58 192.5