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Energy & Chemistry
Energy & Chemistry
SYSTEM
∆E = q + w
∆E = q + w work done
by the
system
energy
change
Energy is conserved!
The First Law of
Thermodynamics
• Exothermic reactions
generate specific amounts
of heat.
• This is because the
potential energies of the
products are lower than
the potential energies of
the reactants.
The First Law of Thermodynamics
• There are two basic ideas of importance for thermodynamic
systems.
1. Chemical systems tend toward a state of minimum potential
energy.
T(system) goes up
T (surr) goes down
ENTHALPY
∆H = Hfinal - Hinitial
If a rxn. is the sum of 2 or more others, the net ∆H is the sum of the ∆H’s
Enthalpy Values
Depend on how the reaction is written and on phases
of reactants and products
H2(g) + 1/2 O2(g) → H2O(g) ∆H˚ = -242 kJ
2H2(g) + O2(g) → 2H2O(g) ∆H˚ = -484 kJ
Specific heat (Cs) — amount of energy needed to Hydrogen gas 14.30 28.82
increase the temperature of 1 g of a substance by Iron solid 0.450 25.1
1°C, units are J/(g•°C)
Lithium solid 3.58 24.8
The quantity of a substance, the amount of heat
transferred, its heat capacity, and the temperature Mercury liquid 0.1395 27.98
change are related in two ways: Nitrogen gas 1.040 29.12
q = nCpΔT where n = number of moles of
substance Neon gas 1.0301 20.7862
q = mCsΔT where m = mass of substance in grams Oxygen gas 0.918 29.38
Uranium solid 0.116 27.7
gas (100 °C) 2.080 37.47
Water liquid (25 °C) 4.1813 75.327
solid (0 °C) 2.114 38.09
All measurements are at 25 °C unless noted. Notable minimums and
Aluminum maximums are shown in maroon text.
Specific Heat Capacity
If 25.0 g of Al cool from 310 oC to 37 oC, how
many joules of heat energy are lost by the Al?
Heat/Energy Transfer
No Change in State
Note that T is
constant as ice melts
or water boils
Thermochemical Equations
• Thermochemical equations are a balanced chemical reaction plus the H value
for the reaction.
– For example, this is a thermochemical equation.
20
15
10 Gases liquefy
before reaching 0K
5
0
0 50 100 150 200 250 300 350 400
Temperature (K)
absolute zero = -273.15 0C
• Gay-Lussac showed that a plot of V versus T was a straight line that could be extrapolated to –
273.15ºC at zero volume, a theoretical state.
• The slope of the plot of V versus T varies for the same gas at different pressures, but the intercept
remains constant at –273.15ºC.
• Significance of the invariant T intercept in plots of V versus T was recognized by Thomson (Lord
Kelvin), who postulated that –273.15ºC was the lowest possible temperature that could theoretically
be achieved, and he called it absolute zero (0 K).
The Combined Gas Law Equation
• Boyle’s and Charles’ Laws combined into one statement is
called the combined gas law equation.
– Useful when the V, T, and P of a gas are changing.
MnO 2 &
2 KClO 3(s)
2 KCl (s) + 3 O 2 ( g)
2 mol KClO3 yields 2 mol KCl and 3 mol O 2
2(122.6g) yields 2 (74.6g) and 3 (32.0g)
At large volumes a and b are relatively small and the van der Waal’s
equation reduces to the ideal gas law at high temperatures and low
pressures.
Real Gases:
Deviations from Ideality
• Calculate the pressure exerted by 84.0 g of ammonia, NH3, in a 5.00 L
container at 200. oC using the ideal gas law.
PV = nRT
P = nRT/V n = 84.0g * 1mol/17 g T = 200 + 273
P = (4.94mol)(0.08206 L atm mol-1 K-1)(473K)
(5 L)
P = 38.3 atm
Real Gases: Deviations from Ideality
• Calculate the pressure exerted by 84.0 g of ammonia, NH3, in a 5.00 L container at 200.
o
C using the van der Waal’s equation. The van der Waal's constants for ammonia are: a
= 4.17 atm L2 mol-2 b =3.71x10-2 L mol-1
n 2a
2
P + V nb nRT
V
nRT n 2a
P - 2
V - nb V
n = 84.0g * 1mol/17 g T = 200 + 273
P = (4.94mol)(0.08206 L atm mol-1 K-1)(473K) (4.94 mol)2*4.17 atm L2 mol-2
5 L – (4.94 mol*3.71E-2 L mol-1) (5 L)2
P = 39.81 atm – 4.07 atm = 35.74
P = 38.3 atm
7% error