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Solutions: Terms
Molarity: moles of solute per liter of solution.
Molality: moles of solute per kg of solvent.
Mole fraction: fraction of moles of given
substance relative to total moles in solution.
Xa = na/n
What is an electrolyte?
Free ions in a solution conducts electricity.
What is the vant Hoff factor, i?
Number of ions existing after dissolution of
one unit of substance: NaCl, CaCl2
Colligative Properties:
Important!
What does a colligative property depend
upon?
Number of solute particles in solution (not
identity of solute) vant Hoff factor comes
up big!
There are three for the MCAT name em:
vapor-pressure depression.
boiling-point elevation.
freezing-point depression.
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Vapor Pressure
Definition?
Sometimes a tough concept pressure
exerted by the gaseous phase of a liquid that
evaporated from exposed surface of liquid.
My definition: pressure exerted by
molecules leaving liquid phase on the
atmosphere lets draw what I mean!
Vapor Pressure
Vapor Pressure
Think about my definitionwhat property of
the liquid will determine vapor pressure?
Intermolecular forces!
High ones will hold liquid in liquid form and
decrease pressure exerted by molecules leaving
liquid.
Low ones will allow liquid to escape into
gaseous form and increase pressure exerted by
molecules as they change phase volatile.
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bimolecular
2NO2
termolecular
unlikely!
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Activation Energy, Ea
Activation energy is the extra kick of
energy that a reaction needs to proceed.
MCAT loves Ea diagrams, but first, what
are exothermic and endothermic reactions?
Two diagrams, one for each above type:
Ea
Ea
R
H _
P
R
H +
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Activation Energy, Ea
From the activation energy concept, three
statements can be made:
Ea1
Ea2
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Catalysts
What is a catalyst?
Substance that makes reaction go faster by
speeding up rate-determining step or providing
an optimized route to products.
Reactant vs. catalyst
catalyst unchanged at
end of reaction.
Catalysts change rate,
not thermodynamics
(G, H, S, etc.).
Ea
Ea,cat
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Rate Laws
What does a rate law tell us?
The rate at which a reactant disappears.
Consists of rate constant, and
concentrations of reactants in slow step
only!!
Rate laws determined experimentally.
aA + bB cC + dDrate law?
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Rate Laws
Rate = k[A]x[B]y
x order of rxn with respect to A.
y order of rxn with respect to B.
x+y overall order of reaction.
k rate constant.
Note: cannot get orders of reactants or rate
constant from balanced equation.
Need to look at experiment to get rate law.
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Rate Laws
A+B+CD+E
Experiment
[A]
[B]
[C]
0.2 M
0.1 M
0.05 M
Initial Rate,
Ms1
1 103
0.4 M
0.1 M
0.05 M
2 103
0.2 M
0.2 M
0.05 M
4 103
0.2 M
0.1 M
0.1 M
1 103
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Rate Laws
Look at two experiments where only one
reactant concentration changes.
Determine the factor by which it changes,
and compare to factor by which rate
changes.
order 1.
[A] doubles rate doubles
[B] doubles rate quadruples order 2.
[C] doubles rate uneffected order 0.
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Rate Laws
When order is 0, rate does not depend on
concentration of reactant.
Rate law for this example: k[A][B]2
Determining kanyone remember the
formula for finding k?
Solve the rate lawk = rate/[A][B]2
Substitute numbers from any experiment for
[A] and [B].
k = 1 103 / 0.2 (0.1)2 = 0.5 Ms1
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Le Chteliers Principle
What does Le Chteliers principle state?
A system at equilibrium will try to neutralize any
imposed change (stress) in order to reestablish
equilibrium.
The effects of different stresses:
Le Chteliers Principle
N2 (g) + 3 H2 (g) ' 2 NH3 (g) + heat
Adding or removing N2
Adding or removing NH3
Reducing volume? Increasing volume?
cut volume, raise pressure favor fewer moles
raise volume, decrease pressure favor greater moles.
Solubility Product
How is the solubility product constant defined?
The extent to which a salt will dissolve in water.
Ksp is determined just like Keq.
Solubility product constant is also temperature
dependent.
MnXm(s) ' nMx+(aq) + mXy(aq)
Ksp = [Mx+]n[Xy]m
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Amphoteric Substances
What is an amphoteric substance?
A substance that can act as either an acid or a
base.
Where does this happen? Polyprotics!
When a substance has more than one proton to
donate, the conjugate base can either donate
another or accept a free proton.
H3PO4 ' H2PO4 + H+ ' HPO42 + 2H+ '
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pH Calculations: A Shortcut
Normal formula: pH = log[H+]also,
pOH = log [OH]
Great when [H+] = 1 102 pH = 2
But how about when [H+] = 2.3 104 M?
Use this shortcut
if [H+] = y 10n M (where n is a whole number).
then pH is between (n1) and n.
pH Calculations
Remember the shortcut for estimating pH
from [H+].
When looking at weak acid (base), given its
initial concentration, use the ICE method to
find [H+] and pH.
What is pH of 0.2 M solution of HCN?
Ka = 4.9 1010
Neutralization Reactions
What is a neutralization reaction?
When an acid and base react to form a salt
and water.
Like when you take antacid (Tums, etc.).
A handy formula for complete neutralization:
a [A] Va = b [B] Vb
a is # acidic H, b is # Hs base can accept.
[X] is acid/base concen. and V is volume.
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Neutralization Reactions
How much 0.1 M NaOH solution needed to
neutralize 40 mL of 0.3 M HCl?
HCl(aq) + NaOH(aq) NaCl(aq) + H2O(l)
a [A] Va = b [B] Vb
1 0.3 40 = 1 0.1 Vb
Solve for Vb to get 120 mL.
Remember the formula to get you out of
jamsworks with neutralization reactions
only to save time over the ICE method.
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Indicators
An indicator marks the endpoint of a titration,
but why does it change color?
Indicator is actually weak acid whose
protonated form is one color and deprotonated
is another.
How does this help us?
Dont forget that the indicator is a weak acid!
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Indicators
HIn ' H+ + In
Ka = [H+][In]/[HIn]now rearrange:
[H+]/Ka = [HIn]/[In]and look at ratios:
If [H+] Ka, [HIn] [In]see color 1
If [H+] = Ka, [HIn] = [In]mix of two colors
If [H+] Ka, [HIn] [In]see color 2
Picking an Indicator
When picking an indicator, use one whose
pKa value lies within the pH range that you
want to detect.
For indicator, pKa +/ 1 represents effective
range for color change.
So dont expect to detect a pH change from
3 to 4 if your indicator has a pKa of 8 or 9!
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Hydrolysis of Salts
The reaction of a substance (salt/ion) with
water is a hydrolysis reaction.
Questionwill the hydrolysis result in a
neutral, acidic, or basic salt?
NaCl in water neutral because neither Na+
nor Cl will react with water:
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Hydrolysis of Salts
NH4CN in waterNH4+ is weak acid, but
CN is good base, so which wins??
Need to know Ka/Kb values!
Ka for NH4+ = 6.3 1010
Kb for CN = 1.6 105
Solution will be basic because CN is better
base than NH4+ is an acid.
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What is a buffer?
A solution that resists changing pH when a
small amount of acid or base is added.
The resistance comes from the presence of a
weak acid or base and its conjugate in
roughly equal concentrations.
An expression to remember:
Ka =
[conj.
+
[H ]
base]
[acid]
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Buffer Compensation
A biochemical example: the blood.
The main buffer: carbonic acid:
CO2 + H2O ' H2CO3 ' H+ + HCO3
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Buffer Compensation
Compensation critical to prevent medical
disorders like acidosis and alkylosis.
Essentially Le Chteliers principle at work.
Addition of small amount of acid like HCl
causes added H+ to react with present HCO3
to form H2CO3.
Equilibrium has shifted to the left, but existing
H2CO3 prevents large change in pH
(compensation reverses effects).
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Buffer Compensation
Provided that acid and its conjugate are in
similar concentration, the pH change is
minimal.
Addition of small amount of base like KOH
causes added OH to react with present H2CO3
to form HCO3.
Equilibrium has shifted to the right, but
existing HCO3 prevents large change in pH
(compensation reverses effects).
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[HA]
pOH = pKb + log
[A]
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HIn GF In
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Buffer!
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Titration Curves SA + SB
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Titration Curves WA + SB
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Titration Curves WB + SA
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Second Law of
Thermodynamics
The Second Law what does it state?
All processes tend to run in a direction that leads
to maximum disorder. If a process is
spontaneous in one direction, then the reverse
cannot be spontaneous makes sense!
From here, we can discuss entropy, enthalpy,
and free energy.
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More Enthalpy
Each reaction has own H doubling reactants
will double the heat required or released.
Hesss Law of Heat Summation, Remember?
If a reaction occurs in several steps, the sum of
the energies absorbed or released in all steps will
be the same as the overall reaction.
If reaction is reversed, the sign of H reverses
too.
If equation multiplied by constant, so too is H.
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= H1 + 2H2 + (H3)
CH4(g)
Hrx = H1 + 2H2
2O2(g)
Hrx = H3
CO2(g) + 2H2O(g)
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G and Temperature
G = H TS
H
Reaction is
Spontaneous
Spontaneous
Non-spontaneous
at high T
+ at low T
+ at high T
at low T
+
Non-spontaneous
Spontaneous
Non-spontaneous
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Oxidation-Reduction Reactions
Oxidation number: how many electrons an atom
is donating or accepting in moleculaar bonding.
Oxidation-reduction (redox) reaction: reaction in
which oxidation numbers of reactants change.
LEO says GER, LEO the GERman, OIL RIG
Oxidation is loss, Reduction is gain of electrons.
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Nernst Equation
2.303RT
0.0592 V
logQ = E
logQ
E = E
nF
n
Electrode potentials for non-standard
conditions, but T still = 298 K.
Zn(s) + Cu2+(aq) Zn2+(aq) + Cu(s)
[Zn2+]
0.0592 V
log
E = E
2
[Cu2+]
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Electrolytic Cells
Unlike a galvanic cell, electrolytic cells use an
external voltage source like a battery to create an
electric current that forces a non-spontaneous
redox reaction to occur electrolysis.
Electroplating: plating a thin layer of metal on top
of another material application of electrolytic
cells, often done in coin mints or with jewelry.
Red cat, an ox still applies!
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Concentration Cells
A galvanic cell that has identical electrodes but
whose half-cells have different ion
concentrations.
Electric current from potential difference arising
from unequal concentrations.
Electrons will flow in direction of highest
concentration of positive ions.
When concentrations of solutions become equal,
the reaction will stop.
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Concentration Cells
[Ni2+]dilute
0.0592 V
log
E = E
2
[Ni2+]concentrated
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