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Kinetics
• Isolated System – does not permit the transfer of both matter &
energy
• Open System – allows the transfer of both matter & energy
• Closed System – does not permit the transfer of matter but allows
the transfer of energy
Intensive property – a system property that can have the same value
for each of the parts
• temperature, pressure, density
Equation of state
- mathematical expression used to describe the state of a system
- must contain the minimum number of variables required to define
the state of a system
- only takes into consideration equilibrium states
- provides only the initial and final states of the system
where:
P1, P2, P3, … , Pi= partial pressures
such that
Pi= xi Ptotal
Internal Energy, U
Total sum of the kinetic and potential energies of a system
Units: 1 J = 1 kgm2/s2 = beat of the human heart
1 cal = 4.184 J
= energy required to raise the temperature of 1g
of water by 1C (14.5 C – 15.5 C)
MatSciPhyChem Engr. SuzzydTE
U = q – W
• + q for endothermic rxn
• - q for exothermic rxn
• +W for work done by the system to the surroundings
• -W for work done on the system by the surroundings
WORK OF EXPANSION:
w force x distance
• work is done by the system
at infinitesi mal dimensions : • V 2 > V1
dw Fdx • w is positive
but F PA
where A is the x - sectional FREE EXPANSION:
area of the piston • expansion against zero
so dw PAdx PdV opposing force
V • w is zero
w V 2 PdV
1
MatSciPhyChem Engr. SuzzydTE
Useful simplifications:
• Constant Volume – Isochoric
• Constant Pressure – Isobaric
• Constant Temperature – Isothermal
• No Heat Flow - Adiabatic
U = q
U = q – pdV
U2 - U1 = q – p (V2-V1)
0=q–W; q=W
W = p dV = (nRT / V) dV = nRT dV / V
W = nRT ln (V2 / V1)
W = nRT ln (P1 / P2)
U = -W
P1V1 = P2V2
T1V1-1 = T2V2-1
T1P1-1 = T2P2-1
= Cp/Cv
MatSciPhyChem Engr. SuzzydTE
A form of energy that when transferred into a system produces a rise
in temperature
q = CT
C p Cv R C p Cv always
Q mcT
Q 0.725kg128J/kg - K 602K - 298K
Q 28.2kJ
H U PV
H q p
Interpretation: Enthalpy change is equivalent to the heat absorbed or
evolved.
MatSciPhyChem Engr. SuzzydTE
Enthalpy is not Heat!!!
“Enthalpy” is sometimes described as the heat content of a system under
a given pressure, whereas "heat" is defined as thermal energy in transit.
p 2
2 2
2 1 2 1
2 1
H rxn
o
H of ( CO 2 ) H of ( CaO ) H of ( CaCO3 )
H rxn
o
151.9 94.05 (288.45)
H rxn
o
42.5kcal / mol
MatSciPhyChem Engr. SuzzydTE
7. Find the enthalpy of the following reaction at 298 K and 1 atmosphere.
MnSiO3( s ) MnO( s ) SiO2 ( quartz )
S system S surroundings 0
S system S surroundings 0
S Sproducts Sreactants
The equation above requires that the entropies of all reactants and
products at the desired temperature is known.
H o
S Tr
TTr
MatSciPhyChem Engr. SuzzydTE
At constant Pressure:
C p dT
dS
T
At constant Volume:
Cv dT
dS
T
MatSciPhyChem Engr. SuzzydTE
If Pressure and Volume are not constant:
Cv dT RdV
S
T V
At constant Temperature:
RdV V2
S R ln
V V1
F U TS
This value is used for constant T and V problems. Mostly used for
chemical reactions/ systems involving pressure changes (such as in
chemical explosives).
G H TS
lL mM qQ rR
the standard free energy change at 25°C is:
G o
298 , reaction G o
298 , products G o
298 , reactants
G o
298 , reaction qG
o
298 ,Q rG o
298 , R lG o
298 , L mG
o
298 , M
Solvent
Component present in the greatest amount;
Also host atoms
Solute
Component present in a minor concentration
Common-Ion Effect
Describes the decrease in solubility of an ionic compound when a
salt that contains an ion that already exists in the chemical
equilibrium is added to the mixture.
a. Solids
• Decrease in solubility if the reaction is exothermic (by Le Chatelier Principle)
• Increase in solubility if the reaction is endothermic
b. Liquids
• No defined trends (less likely to encounter L-L solvent-solute mixture)
c. Gases
• Increase in temperature decreases solubility of gases due to increase of kinetic
energy of gases which eventually cause them to escape to the gas phase
1. Changes in Concentration
⇒ Adding a reactant or product, the equilibria shifts away from the increase in
order to consume part of the added substance.
⇒ Removing a reactant or product, the equilibria shifts toward the decrease to
replace part of the removed species.
Example: For N2(g) + 3H2(g) ↔ 2NH3(g), does the equilibrium shift left or right if the
pressure is increased?
3. Changes in Temperature
Heat can be considered a reactant in an endothermic reaction and a product
in an exothermic reaction:
Endothermic (∆H > 0) Reactant + Heat ↔ Products
Exothermic (∆H < 0) Reactant ↔ Products + Heat
K is larger when the reaction shifts right. This occurs if T is increased for an
Endothermic Reaction or T is decreased for an Exothermic reaction.
K is smaller when the reaction shifts left. This occurs if T is decreased for an
Endothermic Reaction or T is increased for an Exothermic reaction.
MatSciPhyChem Engr. SuzzydTE
Le Chatelier’s Principle
3. Changes in Temperature
4. Effect of a Catalyst
⇒ Catalysts lower the activation energy for the reaction, so a catalyst
decreases the amount of time taken to reach equilibrium for both the forward
and reverse reactions.
⇒ The catalyst does not affect the equilibrium concentrations of reactants and
products in the equilibrium mixture; thus, K value does not change.
…and so forth.
MatSciPhyChem Engr. SuzzydTE
MatSciPhyChem Engr. SuzzydTE
Time required to decrease the concentration of the reactants to half
its initial value
Zero-order:
First-order:
Second-order:
or
(a) For the reaction above, find the rate constant at 25°C if the initial rate is 28 mol/L-s
when the concentration of nitric oxide is 0.20 mol/L and the concentration of
oxygen is 0.10 mol/L.
(b) Calculate the equilibrium constant for the reaction at 25°C.
MatSciPhyChem Engr. SuzzydTE
MatSciPhyChem Engr. SuzzydTE
– branch of science that examines the phenomena resulting from
combined chemical and electrical effects
– study of systems in which electricity plays a role in the changes that
occur during a reaction
Redox reaction
– a chemical reaction wherein a transfer of electrons takes place
• Reduction = gain of electrons
(The substance reduced is the oxidizing agent)
• Oxidation = loss of electrons
(The substance oxidized is the reducing agent)
MatSciPhyChem Engr. SuzzydTE
Two types of electrochemical processes:
1. Electrolytic processes
– Reactions in which chemical changes
occur on the passage of an electrical
current
2. Galvanic or Voltaic processes
– Chemical reactions that result in the
production of electricity
– Galvanic Cell = A device in which chemical
energy is changed to electrical energy
Oxidation occurs at the anode
Reduction occurs at the cathode
Voltage (V)
• defined as the amount of energy (J) that can be delivered per
unit of charge (C) as the current moves through the circuit
• 1 V = 1 J/C
SRP = Oxidized
SRP = Reduced
Since, ΔG = ΔG° + RT ln Q
Hence,
Nernst Equation
23. Devise the cell with the reaction below and calculate the standard emf:
2Na (s) + 2H2O (l) 2NaOH (aq) + H2 (g)
24. Calculate the equilibrium constants of the following reactions at 25°C from
standard potential data:
Sn (s) + CuSO4 (aq) Cu (s) + SnSO4 (aq)
25. How long must a current of 5.00 A be applied to a solution of Ag + to produce 9.7 g
of silver metal?
MatSciPhyChem Engr. SuzzydTE