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Thermochemistry
─the First Law
1. General Conceptions
2. The First Law of Thermodynamics
3. Enthalpy and the Enthalpy of Chemical
Change
4. Thermochemical Equations
1. General Conception in Thermodynamics
1 cal = 4.184 J
Heat is not a State Function
1 1
Q m Cs T = 100 g 4.18J K g 5K 2kJ
The other way: stir the water vigorously with paddles until 2
kJ of work has been supplied.
Q0
U 0
Surroundings Surroundings
Energy Energy
System System
Q >0 Q <0
Heat and Work
W F d
= Pex A d
Pex V
W Pex V
convert the units to joules use 101.325 J = 1 atm∙L
Free Expansion : Pex 0 (vacuum), W 0
Sign conventions
Sign When
heat + heat transferred from surroundings to
system (temperature of system often
increases).
- heat transferred from system to
surroundings (temperature of
surroundings often increases).
work + work is done on system
- work is done by system
If a balloon is inflated from 0.100 L to 1.85 L against an
external pressure of 1.00 atm, how much work is done?
Find: w, J
P, V
Concept Plan:
w
w - P V
Relationships: 101.3 J = 1 atm L
Solution:
V V2 V1 w P V 1.75 atm L
101.3 J
V 1.85 L - 0.100 L 1.00 atm 1.75 L
1 atm L
1.75 atm L - 177 J
1.75 L
Check:
the unit and sign are correct
2. The First Law of Thermodynamics
l Q
U1 U
W 2
Pex U2 = U1 + Q + W
U Q W
Q: heat flow in to the system is positive
heat flow out of the system is negative
-740. kJ
H U PV
At constant pressure and with no nonexpansion work.
H U PV
Q W PV
Q Pex V PV
Qp
Note:
H is a state function, a property of a system that
depends only on its present state and is independent of
any previous history of the system, or independent of path.
H U nRT , H U nRT
Endothermic and Exothermic Reactions
Heat Heat
System System
H >0 H <0
N 2 (g ) 3H 2 (g ) 2NH 3 (g ); H -91.8 kJ
1. In a thermochemical equation it is important to note
phase labels because the enthalpy change, H, depends
on the phase of the substances.
2H 2 (g ) O 2 (g ) 2H 2O(g ) ; H - 483.7 kJ
o
2H 2 (g ) O 2 (g ) 2H 2O(l ) ; H - 571.7 kJ
o
2S(s ) 3O 2 (g ) 2SO 3 (g ); H o ?
If we multiply the first equation by 2 and reverse the
second equation, they will sum together to become the
third.
H 906 kJ
o