ANALYTICAL SEPARATIONS
Download
Report
Transcript ANALYTICAL SEPARATIONS
Chapter 17
THERMODYNAMICS
What is Thermodynamics?
Thermodynamics is the study of energy changes that
accompany physical and chemical processes.
Word origin:
“Thermo”, from temperature, meaning heat
“Dynamics”, which means motion (under the action of forces)
Chemical thermodynamics answers the questions:
How much heat is evolved during a chemical reaction
("thermochemistry")?
What determines the direction of spontaneous chemical
reactions?
Spontaneous Processes
A spontaneous process occurs by itself without any ongoing
outside intervention
Examples: A cube of ice melting in water; a steel pipe rusting;
Spontaneous chemical reactions behave the same way
Reaction continues until equilibrium is reached
If a reaction is spontaneous in one direction, it is not
spontaneous in the other
Spontaneity has nothing to do with rate/speed of reaction
Spontaneity versus Speed/Rate
Spontaneous; 1 atm, 25 0C
C Diamond
C Graphite
Nonspontaneous; 1 atm, 25 0C
Spontaneous = Thermodynamically
favorable; Large Keq)
BUT…
Extremely slow = Kinetically
unfavorable; Small rate)
Spontaneous ≠ Instantaneous (Fast)
Spontaneous Processes
If a reaction is spontaneous in one direction, it is not
spontaneous in the other
Diamond to graphite: Spontaneous (but extremely slow)
at room T
Graphite to diamond: Nonspontaneous at room T (otherwise
we’ll all be rich!)
Melting of ice cube at room T is spontaneous, but freezing of
water at room T is not spontaneous.
In the examples above energy is conserved (1st law). Yet one
process occurs while the other does not.
Spontaneous Processes (Cont.)
Spontaneous processes may need a little “push” to get started
Example: Hydrogen and oxygen gases burn spontaneously
only after being ignited by a spark
2H2 (g) +
O2 (g)
2H2O(l)
The reverse reaction is nonspontaneous (i.e. Water does
not simply decompose into H2 and O2 gases)
Nonspontaneous reactions
Can we make nonspontaneous reactions happen?
Yes. It happens everyday. HOW?
By supplying energy
Examples:
Photosynthesis (CO2 (g) + H2O (l) = Carbohydrates) takes
place upon absorption of solar energy
The nonspontaneous reaction
2H2O(l)
2H2 (g) +
O2 (g)
happens if we pass electricity through water (electrolysis)
Factors Affecting Spontaneity
1. Changes in enthalpy (ΔH)
a) Exothermic reactions ( - ΔH) → tend to be
thermodynamically favorable [ large Keq]
b) Endothermic reactions ( + ΔH) → tend to be unfavorable
Example: All combustion reactions (such as the combustion of
natural gas or methane) are spontaneous and exothermic.
CH4 (g) +
2O2 (g)
Methane
Spontaneous and
Exothermic (- ΔH)
CO2 (g)
+
2H2O (g)
ΔHrxn0 = - 802 kJ
Factors Affecting Spontaneity – Cont.
NOTE: Not all exothermic reactions are spontaneous
Examples of endothermic reactions that are spontaneous
Vaporization of water (+ΔH) at ordinary T and P
Dissolving of NaCl in water (+ΔH)
Thus, the sign of ΔH does not always predict
spontaneous change
Q. What other factor affects direction of spontaneous
reactions?
Factors Affecting Spontaneity – Cont.
2. Changes in entropy (ΔS) or degree of “disorder”
Recall: Entropy (S) is a measure of the dispersal of energy as
a function of temperature
Closely associated with randomness or disorder
a) Increase in entropy ( + ΔS) or disorder → tend to be
favorable [ large Keq]
b) Decrease in entropy ( - ΔS) or more order → tend to be
unfavorable
The “Randomness” Factor
In general, nature tends to move spontaneously from a
more ordered state to more random (less ordered) state .
Randomness also predicts
spontaneous processes
An example of a + ΔS
What? Are you expecting your room to
become more ordered in time?
http://www.lecb.ncifcrf.gov/~toms/
molecularmachines.html
Factors Affecting Spontaneity – Cont.
Change to more disordered (more random) state
= Increase in entropy (+ ΔS)
Q. Which of the two images below has a + ΔS? Is spontaneous
above 0 0C?
Image source:
http://demo.physics.uiuc.edu/Lect
Demo/scripts/demo_descript.idc?
DemoID=1114
MELTING
More disorder =
higher entropy (+ ΔS)
Spontaneous when T > 0 0C
Entropy (S) is a State Function
Recall that entropy is a state function:
Depends only on the initial and final states of the
system (Not on path taken from one state to another)
ΔS = Sfinal - Sinitial
For a chemical reaction, entropy change is expressed as:
ΔSrxn = ∑ n x ΔSproducts - ∑ n x ΔSreactants
In general:
ΔS gas > ΔS liquid > ΔS solid
Most
disordered
Most ordered
(Least disorder)
Entropy (S) and Phase Changes
Exercise: Predict the sign of ΔS in each of the following
processes.
Freezing
- ΔS
Vaporization
+ ΔS (becomes more disordered)
Condensation
- ΔS
Reactions that produce gas (+ ΔS)
tend to be favorable
Entropy and the 2nd Law of Thermo.
Second law of thermodynamics: In a spontaneous process
there is a net increase in the entropy of the universe*
Layman’s term: All real processes occur spontaneously in the
direction that increases disorder.
*
Universe = System + Surrounding
Thus,
ΔSuniverse = ΔSsystem +
ΔSsurrounding
A process (or reaction) is spontaneous if ∆Suniverse is (+)
Entropy and the 2nd Law of Thermo. – Cont.
ΔSuniverse = ΔSsystem +
ΔSsurrounding
Q. When is ∆Suniverse positive?
(+) ∆Suniverse when: ΔSsystem + ΔSsurrounding > 0
If this decreases, ∆Ssurr. must increase even more to offset the
system’s decrease in entropy
Example: During growth of a child, food molecules (carbs,
proteins, etc) are broken down into CO2, water and energy
Increases ∆Ssurrounding
Exothermic ( -∆H)
But formation of body mass decreases ∆Ssystem
Thus, ↓ ∆Ssystem is offset by ↑ ∆Ssurrounding = Still obeys 2nd law
Entropy and the 3rd Law of Thermo.
Q. What happens to a system if we decrease the temperature
continuously?
Entropy will decrease (more order)
Recall: ∆S (g) > ∆S (l) > ∆S (s)
Third law of thermodynamics: The entropy of a pure
crystalline substance at 0 K is zero.
= System
All motion/vibration at absolute zero has stopped
Particles in highest order
Ssystem = 0 at T = 0 K
Entropy and 3rd Law - Cont.
It follows that as the temperature of a system increases, its
entropy also increases.
Thus, T (related to ∆H) and entropy (∆S) both influence
spontaneous reactions
∆H can be measured using a calorimeter
How is ∆S measured?
Standard Molar Entropies, S0
Standard Molar Entropy, S0
Entropy (S) at standard conditions of 1 atm pressure
and 25 0C temperature for one mole of a substance
Unit for S0: J/mol•K
NOTE: Be able to calculate ΔS0rxn from given S0 values
ΔS0rxn = ∑ n x ΔS0products - ∑ n x ΔS0reactants
Table 17.1: Standard molar entropies of substances
Elements and compounds have (+) S0
Aqueous ions may have (+) or (-) S0
Gibbs Free Energy, G
So far you’ve learned that both ∆H and ∆S affect reaction
spontaneity
Is there an equation that relates these two thermodynamic
quantities?
At a constant temperature, the free energy change, ΔG, of a
system is given by the Gibbs-Helmholtz equation:
ΔG
Free energy
change
=
ΔH - TΔS
Enthalpy
change
Kelvin T * Entropy
change
Standard Free Energy Change, ΔG0
The standard free energy change, ΔG0, applies to standards
states as follows:
(1) 1 atm pressure for pure liquids and solids
(2) 1 atm partial pressure for gases
(3) 1 M concentration for solutions
Mathematically:
ΔG0 = ΔH0 - TΔS0
Importance of Free Energy Change:
The sign of ΔG0 determines reaction spontaneity
Importance of ΔG0
The sign of ΔG0 determines reaction spontaneity
(1) - ΔG0 = spontaneous reaction*
(2) + ΔG0 = nonspontaneous reaction
(3) ΔG0 = 0 for reactions at equilibrium (occurs in either
direction)
*At
a constant T and P, reactions go in the direction that
lowers the free energy of the system.
ΔG0 and Spontaneous Reactions
Q. Just when is a reaction spontaneous by looking at ΔG0?
ΔG0 = ΔH0 - TΔS0
Source: Principles of General Chemistry by Silberberg, © 2007.
ΔG0 versus ΔG
ΔG0 vs. ΔG
ΔG0 = free energy of the system at standard conditions
[Pgas = 1 atm; [ ] = 1 M for species in solution (aq)]
Fixed during a reaction under std. conditions
ΔG = free energy of the system at any given condition
[i.e. at any point in the reaction]
Changes during a reaction
Importance of ΔG0
For a given chemical reaction aA + bB → cC + dD
the free energy of the reaction is given by the equation
∆G = ∆G0 + RT ln Q
Reaction quotient
Std. free
energy
Gas
constant
Kelvin
temp.
Q=
[C]c [D]d
[A]a [B]b
Importance of ΔG0 – Cont.
At equilibrium, reaction seem to have stopped (ratefwd = raterev.)
and:
At equilibrium ∆G = 0 ; Q = Keq
∆G = ∆G0 + RT ln Q
= Keq
=0
Thus,
or
0 = ∆G0 + RT ln Keq
at equilibrium ∆G0 = - RT ln Keq
or Keq
(∆G0/RT)
=e
Importance of this equation:
Allows us to calculate ∆G0 given Keq or Keq given ∆G0