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Thermodynamics Long Notes
Thermodynamics Long Notes
Energy
Oxtoby, Chapter 10 (10.1-10.4) (c) isolated
Surroundings Stanford Chemistry
Summer Session 2005 Chem 31
The Basic Concepts: state and path fns The Conservation of Energy:
A state function, X, is a property that depends only on the current state
of the system, and not on how it was prepared.
Changes in a state function depend only on the start and end
Energy can neither be created not destroyed
points of an experiment (experimental observation)
DX = Xfinal – Xinitial
e.g. the duration of this lecture depends only when I start and fl Energy is a state function
when I finish
A path function, Y, is a property that depends on the history of the
system. The principle of conservation of energy can be used to assess
e.g. the boredom/interest factor for this lecture depends on a lot the energy changes that accompany physical and chemical
more than just my first and last sentence processes.
C + O2 CO2 + heat
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Work, Heat and Energy Heat, q
When piston moves out Processes that absorb energy as heat are endothermic;
against higher pressure,
A + heat B
work will be done
Melting, Vaporization of Water
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Work, and pressure +/-? The Sign Convention
w = - pext ∆ V
For pext = 0
Work done by the system on its surroundings is “lost” by the
system (a negative w).
Expansion ∆ V > 0 Compression ∆ V < 0 Work done on the system by the surrounding increases the
internal energy (positive w) – energy is stored in the system
Example: Recall:
Calculate the work done when 25g of iron reacts with Hydrochloric Acid ∆E = w + q
in (a) a closed cell, (b) in a open beaker at 25oC?
& w = - pext ∆V
(a) ∆ V = 0 w=0
If the system is kept at constant volume:
(b) Fes + 2 HCl(aq) FeCl2 (aq) + H2(g) ∆E = qv
w = - pext ∆ V ∆ V = Vf-Vi =Vgas pV = nRT n= m/M We measure ∆E usually using Calorimetry (the measurement
25g mol of amounts of heat flowing into or out of a system and the
w = - pext ∆ V = - pext Vgas = - n R T 55.845 g accompanying temperature changes)
= 0.45 mol
- 0.45mol x 8.314 J x 298 K
w= = - 1.2 kJ
K mol
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Calorimetry Examples
Adiabatic Bomb Calorimeter Adiabatic means no heat is transferred (a) When 100 g of Napthalene was burned in a bomb calorimeter
from calorimeter to surroundings releasing heat of 3.91 kJ, the temperature rose by 3.01 K. What is the
calorimeter constant?
The change in temperature, ∆T, of the
calorimeter is proportional to the heat q = Ccal ∆T 3.91 kJ = Ccal µ 3.01 K
that the reaction releases or absorbs. Ccal = 1.30 kJ / K
q = Ccal ∆T
(b) 10.0 A from a 12 V battery were passed through the heater of a
Calorimeter Constant calorimeter for 150 s. The temperature rose by 5 K. What is the
Calibrated using a process of known energy output calorimeter constant?
(eg, burning of a substance of known mass) or
from an electrical current, I, of known potential, V
q = (10.0 A) µ (12 V) µ (150 s)=1.8 µ 104 A V s = 18 kJ
q=VIt 18 kJ = Ccal µ 5 K Ccal = 3.6 kJ / K
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Heat Capacity Heat Capacity
q
Generally: C = Units: J K-1, cal K-1 1 cal = 4.184 J
∆T
Molar Heat Capacity (J K-1 mol-1 or cal K-1 mol-1)
q C Heat capacity of a sample divided by the
c= =
∆T n n chemical amount of substance, n
Recall: ∆E = w + q
& w = - pext ∆V
If the system is kept at constant volume:
Enthalpy ∆E = qv
But if it is not kept at constant volume?
∆E = qv
Another type of energy, the ENTHALPY, is useful in these
circumstances
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The Enthalpy, H Example: Relating ∆H and ∆U
The internal energy change when 0.500 mol calcite (ρc =2.71 g cm-3)
converts to aragonite (ρa =2.93 gcm-3) is 0.100 kJ. Calculate the
For a system kept at constant pressure:
difference between the changes in enthalpy and in internal energy at a
∆H = qp where ∆H = Hf - Hi pressure of 1 atm. [calcite and aragonite are different forms of CaCO3]
H = U + pV
∆H = ∆(U+pV)=Hf - Hi = (U+pV)a - (U+pV)c
The Enthalpy, like the internal Energy, is a state function = Ua - Uc + (pV)a -(pV)c
= ∆ U + p ∆V as p = const.
m
The Enthalpy is related to the Energy by: ∆H- ∆U = p ∆V Va = ρ a
a
H = U + pV = U + nRT Ma = Mc = 100 g/mol Va = 17.0 cm3
for an ideal gas ∆H- ∆U = 0.152 J ma = mc = 50.0 g Vc = 18.5 cm3
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Rules for enthalpy changes (1) Rules for enthalpy changes (2)
Enthalpy is a state function fl can derive some rules A change in enthalpy is independent of the path taken
between two states:
∆Hovap(373 K)= + 40.7 kJ mol–1 Initial state Final state
vaporisation Sublimation H2O(s) H2O(g)
(1) H2O(l) H2O(g)
condensation ∆Hosub
solid gas
∆Hocond(373 K)= - 40.7 kJ mol–1 ∆Hofus ∆Hovap
solid gas
In general: ∆Ho(A→B) = - ∆Ho(B→A)
the enthalpy of a forward process differs from that of the backwards ∆Hosub = ∆Hofus + ∆Hovap
process only in sign.
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C6 H6 + 7.5 O2 6 CO2 + 3 H2O -3268 kJ/mol 6 C(s, graphite) + 3 H2(g) C6 H6(l) ∆Hof = + 49 kJ/mol
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Bond enthalpies Applications of bond enthalpies
Using average bond enthalpies, estimate the enthalpy change for
A–B(g) A(g) + B(g) ∆Hrxn = energy of the A–B bond
C3H8(g) + 5 O2(g) 3 CO2(g) + 4 H2O(g)
But bond enthalpies are affected by the neighbouring bonds
CH4(g) CH3(g) + H(g) ∆H = 439 kJ mol–1 Step 1: what bonds are in the reactants (draw Lewis structures)
C2H6(g) C2H5(g) + H(g) ∆H = 410 kJ mol–1
C3H8(g) H H H
CHCl3 (g) CCl3(g ) + H(g) ∆H = 380 kJ mol–1
H C C C H
O2
fl usually tabulate average bond enthalpies (determined from A–B H H H O O
bond enthalpies in many different A–B containing molecules)
1 µ (8 C-H bonds),
5 µ (1 O=O double bond)
1 µ (2 C-C bonds)
Average bond enthalpies can be used to estimate the enthalpy of a
compound: just count the number and type of bonds involved. nb: angles are not 90o
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Step 3: calculate the net breakage / formation of bonds: energy is Bond enthalpies appear to give a 30% error!
absorbed in breaking reactant bonds, and released it in making them • Works better when not all bonds are being broken (1st, 2nd, 3rd and
DHrxn º 8H(C–H) + 2H(C–C) + 5H(O=O) 4th C–H bonds in methane have very different strengths)
– 6H(C=O) – 8H(O–H)
• better to use thermochemical groups bonded to at least two other
atoms rather than individual bonds
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Spontaneous Changes:
Why do some processes happen spontaneously?
•Why does a hot body get cooler (rather than hotter) when
surrounded by a cooler medium?
Entropy •Why does a gas expand into all available volume of a container
rather than contract?
Chapter 11
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No process is possible in which the sole result is the absorption of heat Entropy, S, and the second law
from a reservoir and its complete conversion into work.
These spontaneous changes happen because they increase the
randomness with which energy is spread through an isolated system
Kinetic energy converted Energy is not accumulated in ball
into thermal motion and thermal motion is not directional
The Entropy, S, a thermodynamic state function, is a measure of
“molecular disorder”, or “freedom of movement” molecules have, and
helps us to define the direction of spontaneous change
This introduces the idea that changes can be reversible, i.e. a change DS = qrev / T = DH / T (at constant pressure)
can be made, and then exactly undone (“reversed”), so For an irreversible process
∆Suniverse = 0 for a reversible process DS > qrev / T
Entropy
increases ??
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Spontaneous Freezing Entropy of Phase Changes
Solid
∆Hfus Liquid
decreases increases ∆SSysfus =
TFus
∆Ssystem + ∆Ssurroundings = ∆Suniverse > 0 ∆Hvap
similarly, for vaporization ∆SSysvap =
Entropy is not the final determinant of spontaneity — see tomorrow Tvap
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Example: mixing of two gases (pure O2 and pure N2) The chance that you win heads twice is ¼, as it is to win tails twice;
the mixed result has a probability of ½
To quantify S, see microstate considerations below
Tail/Tail Tail/Head or Head/Tail Head
# 1 2 1
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For three throw Similarly for particles in boxes
T/T/T TTH,THT,HHT HHT,HHT,THH H/H/H Imagine you have four balls and can put them into two containers (T or
H) then you can distribute them as follows;
# 1 3 3 1
# 1 4 6 4 1
T H T H T H T H T H
Even split most favored
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The Gibbs Free Energy, G
∆Suni = ∆Ssystem + ∆Ssurroundings
G is a state function
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The Gibbs Free Energy: criterion for spontaneity Criterion for Spontaneity
Examples ∆G = ∆H - T ∆S
∆G < 0 for spontaneous
Remember ∆Gsys < 0 for spontaneous processes
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∆G = ∆H - T ∆S ∆G = ∆H - T ∆S
∆G < 0 for spontaneous ∆G < 0 for spontaneous
3) An exothermic process in which entropy decreases (freeze water) 4) An endothermic process in which entropy increases (melting ice)
Depends on relative Depends on relative
∆H = - ve (<0) magnitudes of ∆H and -T ∆H = + ve (>0) magnitudes of ∆H and -T
∆S ∆S
∆S = - ve ; -T ∆S = + ve (>0) ∆S = + ve ; -T ∆S = - ve (<0)
|∆H| < |T ∆S| |∆H| = |T ∆S| |∆H| > |T ∆S| |∆H| < |T ∆S| |∆H| = |T ∆S| |∆H| > |T ∆S|
T > Tfrze ∆G = ∆H - T ∆S Where o as before indicates that all substances are in their standard
states at the specified temperature.
∆G > 0 Spontaneous Melting of Ice
∆Gro = ∆ Hro - T ∆ Sro
Clearly, the spontaneity of freezing (negative ∆S and negative ∆H)
depends on a balance of the entropy and enthalpy
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Standard Molar Gibbs Energy of Formation Example:
By analogy with the definition of the standard molar Enthalpy of Pt (NH3)2I2, cis Pt (NH3)2I2, trans
formation we define
∆ Sfo = So(Pt(NH3)2I2) - So(Pt(s)) - 2 So(NH3,(g)) - So(I2,(s)) N.B. both ∆G and Q can be used to (PC)c (PD)d
determine the direction of change: Q= (PA)a (PB)b
-0.5425 kJ/(K mol)
∆G | 0
So(Pt(NH3)2I2)cis = 17.9 J/(K mol) So(Pt(NH3)2I2)trans = 21.3 J/(K mol) Q | K
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∆G<0
Q<K Not spontaneous to K2 ∆Hro
∆G>0
Q>K
reactants ln
K1 = R ( 1T 1
1
T2 )
reactants products
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Example:
Similarly, for liquid-vapour equilibrium Water boils at 373.15K at an atmospheric pressure of 1.0 atm.
Calculate the boiling temperature of water on top of Mt Everest
(assuming a pressure of about 0.36 atm). The enthalpy of
The Clausius-Clapeyron Equation vaporization of water can be assumed to be 40.7 kJ/mol.
P2 ∆Hvapo 1 1
ln = (T ) ∆Hvapo 1
P1 R 1 T2 ln P2 = ( T1 1
)
P1 =1.0 atm P2 = 0.36atm
P1 R T2 T1 = 373.15 K
assuming ∆S & ∆ Hro independent of temperature
∆Hvapo = 40.7 kJ/mol
This expression is particularly useful when you want to determine the 0.36 atm
8.314 J ln 1
boiling points of substances at different pressures. 1 atm 1 1
= =
K mol 40.7 103 J mol-1 373.15 K T2 346 K
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