Heating and cooling curves
Starting with a solid below its melting point the follow effects can be observed.
1. The temperature of the solid __________________________ until it begins to melt.
2. When melting begins the temperature ____________________ the solid has all turned into a liquid.
3. The temperature of the liquid ____________________________ until it begins to boil.
4. When boiling begins the temperature _____________ until the liquid has all turned into a gas.
5. The temperature of the gas_____________________________.
Heating Curve
The heating curve can provide a lot of information.
In the regions where the temperature of the solid, liquid or gas is being increased the____________________________ yield a value for the heat capacity. The specific heat capacity is the heat capacity divided by the _____________________________.
A plateau represents a stage __________________________________ with one another.
The heat (or enthalpy) of fusion can be calculated by dividing the length of the melting plateau by the ______________________________
The heat (or enthalpy) of vaporization can be calculated by dividing the length of the boiling plateau by the ____________________________.
Entropy
1st Law of Thermodynamics
Energy is neither created nor destroyed
The energy of the universe is constant
Energy just changes from one form to another
This law lets us know the energy of the system, but does not give us any information about the direction of the energy flow
Spontaneity
Spontaneous process – _____________________________________________
Spontaneous processes can be ____________
Spontaneity tells us the _________________ energy flow
It tells us NOTHING about the ______ of the reaction
For example…
A ball spontaneously rolls down a hill
It does not spontaneously roll up
If iron is exposed to air, it spontaneously rusts
The rust does not spontaneously turn back into air & iron
Entropy
Entropy (s) ______________________________________________
Think of entropy as the amount of _____
The driving force for a spontaneous process is ________________________
Entropy
The natural progression of things is from ________________
Or from _______________________________
Think of a deck of cards…when you drop one it goes from order to disorder
Think of your room… it goes from order to disorder
Think of entropy as a ___________…not a certainty
The more ways a state can exist, _______________________________
Nature spontaneously proceeds toward those states that have the _______________________________
Entropy
Predict which has the highest entropy
CO2 (s) or CO2 (g)
1 mol of N2 at 1 atm or 1 mol of N2 at 0.001 atm
1 mol of N2 at 0.001 atm
Entropy
Predict the sign of the entropy change for the following…
Sugar is added to water to form a solution
Iodine vapor condenses on a cold surface to produce a liquid
-
2nd Law of Thermodynamics
2nd Law of Thermodynamics – ___________________________________________________________________________________________
Energy is conserved…entropy is _______________
3rd Law of Thermodynamics
The entropy of a perfect crystal at 0K is _______
Free Energy
_______________ – a thermodynamic function equal to the enthalpy minus the product of the entropy and the Kelvin temperature
DG = D H – TD S
A process is only spontaneous in the direction where___________________ive
Example
At what temperatures is the following process spontaneous at 1 atm?
Br2(l) à Br2(g)
DH = 31.0 KJ/mol à 31000 J/mol
DS = 93.0 J/ K mol
Dependence of H & S on Spontaneity
What is the sign for D S?
N2(g) + 3H2(g) à 2NH3(g)
First look at the states…if you go from a solid or a liquid to a gas, you will have a + entropy
In this case, all of the states are the same, so we look at the number of moles
N2(g) + 3H2(g) à 2NH3(g)
1 + 3 vs. 2
The entropy decreases because you go from 4 moles to 2
DS is negative
What is the sign for D S?
4NH3 + 5O2 à 4NO + 6H2 O
9 moles vs. 10 moles
DS increases (+)
Calculating D S
Calculating D S is just like calculating D H
Simply use the Appendix…just look at the column for S instead of H
DS° of any element or diatomic molecule is __________
You must look these up!
Example
Calculate D S for the following reaction:
2NiS(s) + 3O2 (g) à 2SO2 (g) + 2NiO (s)
Example
Calculate D S for the following reaction:
Al2 O3 (s) + 3H2 (g) à 2Al(s) + 3H2 O(g)
Gibbs Free Energy & Chemical Reactions
You can calculate D G in 3 ways…
________________
_________
___________________________________
Example
Calculate DH, DS, & DG at 25°C using the following data…
2SO2 + O2 à 2SO3
Example
2SO2 + O2 à 2SO3
DH = 2(+297)+(0) + 2(-396) = -198 KJ
DS = 2(-248)+ (-205) + 2(257) = -187J/K
DG = D H – T D S
=(-198) – (298 x -0.187)
=-142 KJ
Calculate D G
Using the following data at 25°C
Cdiamond + O2(g) à CO2 (g) DG = -397KJ
Cgraphite + O2(g) à CO2 (g) DG = -394KJ
Calculate DG for the reaction:
C diamond à C graphite
Calculating DG
Methanol is a high octane fuel used in high performance racing engines. Calculate DG for the following reaction
2 CH3OH(g) + 3O2(g) à 2CO2(g) + 4H2O(g)
Given the following free energies of formation:
Calculating DG
2 CH3OH(g) + 3O2(g) à 2CO2(g) + 4H2O(g)
2(163) + 3(0) + 2(-394) + 4(-299)
AP Like Questions
C(s) + CO2 (g) « 2CO(g)
All 3 of the gases above form an equilibrium mixture by the equation above
a. Predict the sign of D S of the reaction & justify your prediction
b. In the table below are data that show the % CO in the equilibrium mixture at 2 different temperatures. Predict the sign of DH & justify
Temp %CO
700K 60%
900K 94%
AP Like Questions
c. Appropriately complete the energy diagram for the reaction by finishing the graph below. Also clearly label D H for the reaction…
AP Like Questions
Will the following be endo or exo?
Boil H2O
Dissolve NH4Cl (gets colder)
Dissolving CaCl2 (gets hot)
Melting ice
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