Thermodynamics | Heat Capacity | Heat

# Thermodynamics: Enthalpy, Entropy & Gibbs Free Energy

Thermo 2

Thermodynamics:

thermo = heat (energy) dynamics = movement, motion

Some thermodynamic terms chemists use: 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 1°C (or 1 K). Specific Heat Capacity: 1 g by 1°C Molar Heat Capacity: 1 mole by 1°C

Thermo 3

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

1 calorie = 4.18 joules
Specific Heats and Molar Heat Capacities
Substance Al Cu Fe CaCO3 Ethanol Water Air Specific Heat (J/°C•g) 0.90 0.38 0.45 0.84 2.43 4.18 1.00 Molar Heat (J/°C•mol) 24.3 24.4 25.1 83.8 112.0 75.3 ~ 29

important to:

engineers

chemists

EXAMPLE: How many joules of energy are needed to raise the temperature of an iron nail (7.0 g) from 25°C to 125°C? The specific heat of iron is 0.45 J/°C•g. Heat energy = (specific heat)(mass)(ΔT) Heat energy = (0.45 J/°C•g)(7.0 g)(100°C) = 315 J
Note that ΔT can be ºC or K, but NOT ºF. When just T is being used in a scientific formula it will usually be kelvin (K).

g.5ºC (a fever of just over 103ºF) for someone who weighs 110 pounds (50 kg). Assume an average body specific heat capacity of 3 J/ºC. Problem: What would be more effective at melting a frozen pipe – hot water or a hair dryer (hot air gun). Why? .Thermo 4 Problem: How much energy does it take to raise the body temperature 2.

Thermo 5 Energy: "The capacity to do work and/or transfer heat" Forms of Energy: Kinetic (Ekinetic = ½mv2) Potential Heat Light (Electromagnetic) Electricity Chemical Nuclear Matter (E = mc2) WORK .

"You can't get something for nothing" . In any process energy can be changed from one form to another. but it can never be created nor destroyed.Thermo 6 First Law of Thermodynamics: The total amount of energy (and mass) in the universe is constant.

We use the symbol ΔH to indicate enthalpy.Thermo 7 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.0 M Temperature is not defined or part of Standard Conditions. . Sign notation (EXTREMELY IMPORTANT!!): +ΔH indicates that heat is being absorbed in the reaction (it gets cold) endothermic −ΔH indicates that heat is being given off in the reaction (it gets hot) exothermic Standard Enthalpy = ΔH° (° is called a “not”) Occurring under Standard Conditions: Pressure Concentration 1 atm (760 torr) 1. but is often measured at 298 K (25°C).

ΔH ° = 0 for any element in its standard state (the f natural elemental form at 1 atm or 1 M) at 298 K.5 kJ/mol .5 kJ/mol elements in their standard states negative sign heat released -.exothermic rxn product (one mole) ΔH° (CO2 ) = f 393. EXAMPLES: C(graphite.Thermo 8 Standard Enthalpy of Formation -- ΔH ° f 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. Also called heat of formation. usually at 298 K (25°C). s) + O2 (g) ΔH° = 0 kJ/mol rxn 0 kJ/mol CO2 (g) 393.

by knowing ΔHf of the reactants and products. we can determine the ΔHrxn for any reaction that involves these reactants and products.Thermo 9 2H2 (g) + O 2 (g) ΔH° = 0 kJ/mol rxn 0 kJ/mol 2H2 O (g) 483.8 kJ/mol Note that we usually will not have you calculate ΔHfº on homeworks or tests – so you generally don’t have to worry about normalizing your answer to a per mole basis. . Hess's Law -.exothermic rxn product (two moles) divide by 2 to put on per mole basis!! ΔH° (H2 O) = f 241.6 kJ/ 2 mol elements in their standard states negative sign heat released -.Adding Reactions The overall heat of reaction (ΔHrxn) is equal to the sum of the ΔHf (products) minus the sum of the ΔHf (reactants): ΔH° = rxn Σ (# eqiv) ΔH° (products) Σ (# eqiv) ΔH° (reactants) f f Therefore.

It works by smothering the fire with "heavier" CO2 that replaces oxygen needed to maintain a fire. for more exotic electrical and chemical fires. 2Mg(s) ΔH° = 0 kJ/mol f + CO2 (g) . Mg will "burn" CO2 ! .602 kJ/mol + C(s) 0 kJ/mol REACTANTS PRODUCTS ΔH° = rxn ΔH° = rxn Σ (# eqiv) ΔH° (products) Σ (# eqiv) ΔH° (reactants) f f Σ (2 eqiv)(-602 kJ/mol) + (1 eqiv)(0 kJ/mol) Σ (2 eqiv)(0 kJ/mol) + (1 eqiv)(-393 kJ/mol) (-393 kJ/mol) ΔH° = (-1204 kJ/mol) rxn ΔH° = (-1204 kJ/mol) + 393 kJ/mol rxn ΔH° = rxn 811 kJ/mol } highly exothermic rxn !! Therefore. however. CO2 is not good.393 kJ/mol 2MgO(s) .Thermo 10 EXAMPLE: CO2 is used in certain kinds of fire extinguishers to put out simple fires.

then we also would have to multiply ΔHrxn for that reaction by the same amount.Thermo 11 You can also add two reactions together to get the ΔHrxn for another new reaction: Calculate ΔH° for the following reaction: rxn C2 H4 (g) + H 2O(l) C 2 H 5 OH(l) ΔH° = ?? rxn Given these two reactions and thermodynamic data: a) C 2 H 5 OH(l) + 3O 2 (g) b) C2 H4 (g) + 3O 2 (g) 2CO2 (g) + 3H 2 O(l) 2CO2 (g) + 2H 2 O(l) ΔH° = -1367 kJ/mol rxn ΔH° = -1411 kJ/mol rxn How to solve: 1) C 2 H 5 OH is on the product side of the first reaction -. ΔH° rxn changes sign!!! 2) Now we can add the two reactions together to give us the desired net reaction: 1 C 2 H 5 OH(l) + 3O 2(g) ΔH° = +1367 kJ/mol 2CO2 (g) + 3H 2 O(l) rxn ΔH° = -1411 kJ/mol rxn ΔH° = -44 kJ/mol rxn If we have to multiply one (or more) of the reactions by some constant to get them to add correctly. .so we want to switch equation a) around to get C 2 H 5 OH also on the product side: 2CO2 (g) + 3H 2 O(l) C 2 H 5 OH(l) + 3O 2(g) ΔH° = +1367 kJ/mol rxn * + C2 H4 (g) + 3O 2 (g) C2 H4 (g) + H 2O(l) 2CO2 (g) + 2H 2 O(l) C 2 H 5 OH(l) note that when we reverse the reaction.

Bomb Calorimeter Stirrer Electrical contacts to initate sample combustion Thermocouple to measure temperature Sample placed inside inner container Water Highly insulated outside container Thick-walled inner container (bomb) to contain combustion of sample (pressurized with O2) In order to use this effectively one must know the heat capacity of the bomb (inner part) and water bath.Thermo 12 Chemists use bomb calorimeters to measure Enthalpies of formation or reaction. . By measuring the temperature increase of the water one can calculate the amount of heat given off during the combustion process.

aq) = −908 kJ/mol f ΔH° (H2S. l) = −286 kJ/mol f ΔH° (SO3. 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) d) 2H2S(g) + 3O2(g) 2SO2(g) + 2H2O(l) . l) = −814 kJ/mol f ΔH° (H2O. g) = −297 kJ/mol f ΔH° (H2SO4. g) = −396 kJ/mol f ΔH° (H2SO4.Thermo 13 Problem: Calculate ΔHrxn for the following reactions given the following ΔH° values: f ΔH° (SO2.

most disordered water . 2. The greater the dispersal of energy or matter in a system.Thermo 14 Entropy The final state of a system is more energetically favorable if: 1. Energy can be dispersed over a greater number and variety of molecules. The dispersal of energy and matter is described by the thermodynamic state function entropy.well ordered structure water vapor . The greater the disorder (dispersal of energy and matter. the higher is its entropy. S. Ice . Adding heat to a material increases the disorder. both in space and in variety) the higher the entropy.more disordered . The particles of the system can be more dispersed (more disordered).

mother nature likes) −ΔS indicates that entropy is decreasing in the reaction or transformation (it's getting less disordered {more ordered} -. • Sign notation (EXTREMELY IMPORTANT!!): +ΔS indicates that entropy is increasing in the reaction or transformation (it's getting more disordered -.0 J/K mol).mother nature doesn't like.Thermo 15 Unlike ΔH. 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. but it does happen) .

a liquid to a gas. or more dramatically. 3) Entropy increases as the number of particles (molecules) in a system increases: N2O4(g) S° = 304 J/K (1 mole) 2NO2(g) S° = 480 J/K (2 moles) The first 3 above are most important for evaluating ΔSrxn.Thermo 16 Qualitative "Rules" About Entropy: 1) Entropy increases as one goes from a solid to a liquid. 250 Solid Gas Liquid Entropy (J/mol) 200 150 100 50 0 phase transitions Temperature (K) 2) Entropy increases if a solid or liquid is dissolved in a solvent. The rules below are for comparing the entropy of individual molecules or materials. .

Thermo 17 4) The Entropy of any material increases with increasing temperature 5) Entropy increases as the mass of a molecule increases S°(Cl2(g)) > S°(F2(g)) S° = 165 J/K•mol S° = 158 J/K•mol 6) Entropy is higher for weakly bonded compounds than for compounds with very strong covalent bonds S°(graphite) > S°(diamond) S° = 5.4 J/K•mol .7 J/K•mol S° = 2.

) of a molecule increases Entropy of a Series of Gaseous Hydrocarbons H H C H H Methane S° = 186 J/K•mol H H C C Acetylene H C H H H C H H H C H S° = 201 J/K•mol S° = 220 J/K•mol H C H H C H H C H H C H H Propane Ethylene H Ethane S° = 230 J/K•mol S° = 270 J/K•mol What are the biggest factors for evaluating ΔSrxn for a chemical rxn? 1) phase change 2) change in # of molecules . # of heavier atoms.Thermo 18 7) Entropy increases as the complexity (# of atoms. etc.

is the entropy of the reaction increasing or decreasing? AgCl(s) a) Ag+(aq) + Cl-(aq) b) H2CO3(aq) c) Ni(s) + 4CO(g) d) H2O(s) e) graphite f) 2Na(s) + 2H2O g) H2S(g) + O2(g) h) 2H2O(l) i) CO2(g) + CaO(s) j) CaCl2(s) + 6H2O(l) k) 2NO2(g) N2O4(g) H2O(l) diamond 2Na+(aq) + 2OH-(aq) + H2(g) H2O + CO2(g) Ni(CO)4(l) H2O(l) + SO(g) 2H2(g) + O2(g) CaCO3(s) CaCl2•6H2O(s) .Thermo 19 Problem: For the following reactions.

Thermo 20 Just as with enthalpies.mol) 218 J/K. one can calculate entropies of reaction.mol) rxn ΔS ° = rxn } entropy is decreasing (reaction is becoming more ordered) . ΔS ° = rxn Σ(# eqiv) S°(products) Σ(# eqiv) S°(reactants) + CO2 (g) 2MgO(s) 27 J/K·mol + C(s) 6 J/K·mol EXAMPLE: 2Mg(s) ΔSf° = 32 J/K·mol 215 J/K·mol REACTANTS PRODUCTS ΔS ° = rxn ΔS ° = rxn Σ (# eqiv) S°(products) Σ (# eqiv) S°(reactants) Σ (2 eqiv)(27 J/K·mol) + (1 eqiv)(6 J/K·mol) Σ (2 eqiv)(32 J/K·mol) + (1 eqiv)( 214 J/K·mol) (278 J/K.mol ΔS ° = (60 J/K.

1) Rxn of sodium metal with water: 2Na(s) + 2H2O 2Na+(aq) + 2OH-(aq) + H2(g) 2) Combustion rxns: 2C2H6(g) + 7O2(g) 2H2(g) + O2(g) 4CO2(g) + 6H2O(g) 2H2O(l) 3) Expansion of a gas into a vacuum xCO2(g) yCO2(s) + zCO2(g) (x = y + z) 4) A salt dissolving into solution: NH4NO3(s) + H2O(l) NH4+(aq) + NO3-(aq) .Thermo 21 Spontaneous Processes A process that takes place without the net input of energy from an external source is said to be spontaneous (not instantaneous).

You can't even break even! Neither entropy (ΔS) or enthalpy (ΔH) alone can tell us whether a chemical reaction will be spontaneous or not.Thermo 22 Second Law of Thermodynamics: In any spontaneous process the entropy of the universe increases ΔSuniverse = ΔSsystem + ΔSsurroundings Second Law (variant): in trying to do work. . An obvious (?) conclusion is that one needs to use some combination of the two. you always lose energy to the surroundings.

"Free" energy refers to the amount of energy available to do work once you have paid your price to entropy. the heat energy released in a reaction. Since this was discovered by J. it indicates that a reaction or process is spontaneous. ΔGº = ΔHº − TΔSº When ΔG is negative. Note that this is not given simply by ΔH.Thermo 23 Gibbs Free Energy The combination of entropy. . Willard Gibbs it is also called the Gibbs Free Energy. The symbol ΔG is used to define the Free Energy of a system. temperature and enthalpy explains whether a reaction is going to be spontaneous or not. A positive ΔG indicates a non-spontaneous reaction.

Thermo 24 ΔG = ΔH − TΔS ΔS + Δ G = negative spontaneous at all temperatures Δ G = ?? spontaneous at high temperatures Δ G = ?? spontaneous at low temperatures 0 + Δ G = positive non-spontaneous at all temperatures ΔH Spontaneous = exoergic (energy releasing) Non-spontaneous = endoergic (energy releasing) .

Thermo 25 Remember that entropies are given in units of J/K•mol while enthalpies and free energies are in kJ/mol. DON'T forget to convert all units to kJ or J when using both ΔS and ΔH in the same equation!! DANGER!! Common mistake!! .

however. 1 atm gas pressure). This indicates that the reaction under these conditions will proceed to make products (spontaneous). ΔG: Standard vs.Thermo 26 ΔGº vs. Non-Standard Conditions Remember that the º (“not”) on ΔGº indicates that the numerical value of ΔGº is based on the reaction at standard conditions (1 M solution concentration. . Although for this rxn. When ΔG = 0 the reaction has reached equilibrium. As the reactants start reacting. Temperature is NOT part of standard conditions! As soon as one has a concentration different than 1 M or 1 atm pressure. Consider the reaction: Initial: 1 atm 1 atm 2SO2(g) + O2(g) ΔGºrxn = −142 kJ/mol 1 atm 2SO3(g) The ΔGºrxn of −142 kJ/mol is for when each gas is present with a concentration of 1 atm. the º “not” goes away and one has ΔG. SO2 is probably the limiting reagent (not enough present to complete the rxn). their concentrations decrease (SO2 twice as fast as O2) and ΔGº turns into ΔG and becomes less negative.

S° (O2) = 205 J/mol•K. S°(O2) = 205 J/mol•K. S°(CO) = 198 J/mol•K 2C(graphite) + O2(g) Problem: Calculate ΔGºf for CO at 298 K.002 KJ/mol•K) ΔGºf = (−393 KJ/mol) − (1 KJ/mol) DANGER!! Common ΔGºf = −394 KJ/mol mistake!! (CO) = −110 KJ/mol. S°(C) = 6 J/mol•K. S° (CO2) = 213 J/mol•K C(graphite) + O2(g) CO2(g) ΔGºf = ΔHºf − TΔSºf Note change in units – J to KJ ΔSºf = Σ Sºprod − Σ Sºreact ΔSºf = (213 J/mol•K) − (205 + 6 J/mol•K) ΔSºf = 2 J/mol•K) ΔGºf = (−393 KJ/mol) − (298 K)(0. ΔHf ° 2CO(g) . S° (C) = 6 J/mol•K.Thermo 27 Example: Calculate ΔGºf for CO2 at 298 K. ΔHf ° (CO2) = −393 KJ/mol.

570 kJ/mol + C(s) 0 kJ/mol REACTANTS PRODUCTS ΔG° = rxn ΔG° = rxn Σ (# mol) ΔG° (products) Σ (# mol) ΔG° (reactants) f f Σ (2 mol)(-570 kJ/mol) + (1 mol)(0 kJ/mol) Σ (2 mol)(0 kJ/mol) + (1 mol)(-394 kJ/mol) (-394 kJ) ΔG° = (-1140 kJ) rxn ΔG° = (-1140 kJ) + 394 kJ rxn ΔG° = rxn 746 kJ } SPONTANEOUS rxn! highly exothermic rxn !! Compare to Δ H ° which was -811 kJ for the same rxn.Thermo 28 Just as with enthalpies and entropies. rxn The "missing" 65 kJ of energy went to ENTROPY ! . ΔG° = rxn Σ (# eqiv) ΔG° (products) Σ (# eqiv) ΔG° (reactants) f f EXAMPLE: 2Mg(s) ΔG° = 0 kJ/mol f + CO 2 (g) .394 kJ/mol 2MgO(s) . one can calculate free energies of reaction.

Based on the data below. 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. the temperature at which this will happen: 0 = ΔH°rxn − TΔS°rxn rearranging to solve for T gives: T = (ΔH°rxn) / (ΔS°rxn) T = (465 kJ/mol) / (0.Thermo 29 Example: To make iron. ΔG° will eventually reach 0 and then go negative & spontaneous. ΔH°rxn = +465 kJ/mol ΔS°rxn = +552 J/molK (or 0. so let ΔG° = 0 and solve for T. this is a non-spontaneous reaction at room temperature.552 kJ/molK) T = 842 K (above this temperature ΔG°rxn will be negative – we will have a spontaneous reaction) .. but it becomes spontaneous at higher temperatures. ΔG°rxn = 0).552 kJ/molK) ΔG°rxn = +301 kJ/mol (at 298 K) ΔG°rxn = ΔH°rxn − TΔS°rxn as we raise the temperature. Assuming that ΔH° and ΔS° do not change much with temperature. calculate the temperature above which the reaction becomes spontaneous (i.e.

g) = −34 kJ/mol a) S(s) + O2(g) SO2(g) b) 2SO2(g) + O2(g) 2SO3(g) c) SO3(g) + H2O(l) H2SO4(l) d) 2H2S(g) + 3O2(g) 2SO2(g) + 2H2O(l) . g) = −300 kJ/mol ΔGºf (H2SO4.Thermo 30 Problem: Calculate ΔGºrxn for the following. aq) = −742 kJ/mol ΔGºf (H2S. g) = −371 kJ/mol ΔGºf (H2SO4. ΔGºf (SO2. l) = −237 kJ/mol ΔGºf (SO3. l) = −690 kJ/mol ΔGºf (H2O.

Thermo 31 Comparisons of ΔHºrxn and ΔGºrxn S(s) + O2(g) SO2(g) ΔSºrxn = +11 J/mol K 2SO3(g) ΔHºrxn = −297 kJ/mol ΔGºrxn = −300 kJ/mol 2SO2(g) + O2(g) ΔHºrxn = −198 kJ/mol ΔGºrxn = −142 kJ/mol SO3(g) + H2O(l) ΔHºrxn = −132 kJ/mol ΔGºrxn = −82 kJ/mol 2H2S(g) + 3O2(g) ΔHºrxn = −1126 kJ/mol ΔGºrxn = −1006 kJ/mol H2SO4(l) 2SO2(g) + 2H2O(l) .

Thermo 32 .

Peck & Stanley. by Whitten. Davis. Thomson Brooks/Cole Publisher. 7th Ed.Thermo 33 From “General Chemistry”. .