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Table of Contents
Calculus Review
Linear Regression (Least Squares Method)
Chemical Kinetics
Rate3
Theories on Reaction Rate 4
Factors Affecting Reaction Rate 4
Methods for Determining the Rate Law 5
Dependence of the Concentration of Reactants with Time (Integrated Rate Laws)7
Gas-Phase Reactions 10
Reaction Mechanisms 13
Nuclear Chemistry
Type of Nuclear Reactions 17
Effect of Radiation on Biological Matter 20
Chemical Thermodynamics
First Law of Thermodynamics (Law of Conservation of Energy) 22
Thermochemistry25
Second Law of Thermodynamics 29
Third Law of Thermodynamics 33
Chemical Equilibrium
Approaches to Equilibrium 33
Molecular Equilibrium 35
Factors Affecting Equilibrium 38
Ionic Equilibria
Theories on Acids and Bases 40
Ionization of Water 41
Strong Electrolytes 41
Weak Electrolytes 42
Polyprotic Acids 42
Salts42
Common Ion Effect 43
Buffer Solutions 44
Acid-Base Indicators 44
Acid-Base Titration 45
Complex Ion Equilibrium 45
Slightly Soluble Salts 45
Factors Affecting Solubility 45
Precipitation46
Dissolution46
Electrochemistry
Electrochemical Cell 47
Thermodynamics of Electrochemical Cells 48
Electrolytic Cells 51
Faraday's Law of Electrolysis 52
Coordination Chemistry
Complex / Coordination Compound 53
Ligands54
Nomenclature of Complexes 55
Isomerism56
Structural Isomers 56
Optical Isomers (Enantiomers) 56
Theories on Bonding 57
Valence Bonding Theory (Localized Electron Model) 57
Crystal Field Theory 58
Reactions60
Applications of Coordination Chemistry 61
Properties
1. y = C y = 0
3. d(u + v) = du + dv
Example: f (x) = 3x2 2x + 4 f (x) = 6x 2
4 10
Example: y = 5x 3 + 2 y = 5 + 4x2 20x3
x x
= 5x 3 4x1 + 10x2
6. Chain Rule
Example: f (x) = (4x2 7x + 13)2 f (x) = 2(4x2 7x + 13)(8x 7)
Examples:
x2
1. xdx = +C
2
2. 3 dx = 3 dx = 3 x0 dx = 3x + C
5 3
3. 5x2 dx = 5 x2 dx = x +C
3
x x
4. 3x2 + 14 dx = 3x2 dx dx + 14 dx
4 4
x3 x2
=3 + 14x + C
3 8
1
= x3 x2 + 14x + C
8
10 12
5. 5 + 2 dv = 5 dx 10v 1 dx + 12v 2 dx
v v
12 1
= 5v 10ln|v| + v +C
1
= 5v 10ln|v| 12v 1 + C
Examples:
4
1. (x + 2) dx
2
4 4
= x dx + 2 dx
2 2
4
x 2
= + 2x
2 2
2 2
4 2
= + 2(4) + 2(2)
2 2
= 16 6 = 10
1
3 1 2
2. 4x + 2x 3x + dx
2
1
1 1 1 1
3 2 1
= 4x dx + 2x dx 3x dx + dx
2
1 1 1 1
1
x x 4
x 1 3 2
= 4 + 2 3 + x
4 3 2 2 1
1
2 3 1
= x4 + x3 x2 + x
3 2 2 1
2 3 1 2 3 1
= (1)4 + (1)3 (1)2 + (1) (1)4 + (1)3 (1)2 + (1)
3 2 2 3 2 2
7
=
3
2t
3. 7t 3 4t1 + 10t2 dt
t
2t
t2 t1
= 7 3t 4ln|t| + 10
2 1 t
2t
7
= t2 3t 4ln|t| 10t1
2 t
7
= (2t) t 3 (2t t) 4 (ln|2t| ln|t|) 10 (2t)1 t1
2 2
2
7 2 2t t
= 3t 3t 4 ln 10
2 t 2t2
21 2
= t 3t 4ln2 5t1
2
Example: x y r = 0.999228
15 18
12.5 15 A = 0.3086
12 14.3 B = 1.176
8 10 Equation: y = 1.176x + 0.3086
13.8 16.5
6.7 8
14.6 17.5
Chemical Kinetics
- branch of chemistry that deals with rates or speeds of reaction
- determines the factors that affect rates and its mechanisms
Rate
- in chemistry rate is
1
For the reaction: N2 O5 2N O2 + O2
2
1 d[N O2 ] d[O2 ] d[N2 O5 ]
Rate of reaction = =2 =
2 dt dt dt
d[H2 O] 6 d[N O] 6
1: = = (0.60M/s) = 0.090M/s
dt 4 dt 4
d[O2 ] 5 d[N O] 5
2: = = (0.60M/s) = 0.075M/s
dt 4 dt 4
d[N H3 ] 4 d[N O] 4
3: = = (0.60M/s) = 0.060M/s
dt 4 dt 4
1 d[N O] 1
4: Rate of reaction = = (0.60M/s) = 0.015M/s
4 dt 4
Ea, rate
Example:
Given: A+2B C
a. Rate Law
rate = k[A]x [B]y
b. Differential Method
Example:
[A] [B] Initial Rate (M/s)
0.020 M 0.020 M 8.40 105
0.020 M 0.025 M 1.31 104
0.020 M 0.030 M 1.89 104
0.020 M 0.035 M 2.57 104
0.025 M 0.030 M 2.36 104
0.030 M 0.030 M 2.83 104
0.035 M 0.030 M 3.30 104
rate = k[A]x [B]y
Plot log rate vs log [A] Plot log rate vs log [B]
r = 0.99999 r = 0.999998
B = 0.996 1 = x B = 1.99 2 = y
A = 2.032 = log k[B]y A = 0.679 = log k[A]x
rate = k[A][B]2
[C2 O2
4 ]: at constant [HgCl2 ] [HgCl2 ]: at constant [C2 O2
4 ]
log rate = log k[HgCl2 ] +x
y log[C2 O42 ] log rate = log k[C2 O42 ]y + x log[HgCl2 ]
d[A]
rate = k[A]n rate =
dt
d[A]
= k[A]n
dt
d[A] d[A]
n=0: = k[A]0 n=1: = k[A]1
dt dt
[A]t
t [A]1 d[A] = k dt
d[A] = k dt [A]t
t
1
[A]0 0 [A] d[A] = k dt
[A]t [A]0 = k(t 0) [A]0 0
Example:
Given: 2C5 H6 C10 H12 [A]0 = 0.0400 M
1: Order of Reaction
n=0: Plot [A] vs t rn=0 = -0.967
n=1: Plot ln [A] vs t rn=1 = -0.9905
1 The reaction is a second-order reaction.
n=2: Plot vs t rn=2 = 0.999776
[A] rn=3 = 0.995
1
n=3: Plot vs t
[A]2
2: k slope = k = 0.163 M 1 s1
Half-Life t1/2
- time required to reduce the concentration of the reactant to half of its initial value
ln[A]t = kt + ln[A]0
[A]t = kt + [A]0
1
1 ln [A]0 = kt 12 + ln[A]0
[A]0 = kt 12 + [A]0 2
2
1 1
kt 12 = [A]0 [A]0 kt 12 = ln[A]0 ln [A]0
2 2
n = 0: kt 1 = 1 [A] n = 1: [A]0
2 2
0 kt 12 = ln 1
2 [A]0
[A]0
t 12 = ln 2
2k t 12 =
k
t 12 [A]
t 12 independent of [A]
1 1 [A]0
= kt +
[A]t [A]0 n = 0 : t 12 =
1 1
2k
1 = kt 12 +
[A]0
ln 2
2 [A] 0 n = 1 : t 12 =
2 1 k
= kt 12 1
[A]0 [A]0 n = 2 : t 21 =
n = 2: 1 k[A]0
= kt 12
[A]0
1 20 s 1 10 s 1 5s 1
n = 0 : 1M M
t 12 = M M
k[A]0 2 4 8
20 s 1 20 s 1 20 s 1
n = 1 : 1M M M M
2 4 8
1 20 s 1 40 s 1 80 s 1
t 12 n = 2 : 1M M M M
[A] 2 4 8
Examples:
t= = 27.84 min
(0.0578 min1 )
c. 10% remaining: [A]t = 0.10[A]0
[A]t
ln = kt
[A]0
(0.10)[A]0
ln = (0.0578 min1 )t
[A]0
ln (0.10)[A]
[A]0
0
t= = 39.84 min
(0.0578 min1 )
1 1
= (0.0719 M 1 min1 )t +
0.50 M 0.90 M
1 1
0.50 M 0.90 M
t= = 12.36 min
(0.0719 M 1 min1 )
b. half-life when [HI] is 0.90 M
1 1
t 21 = =
k[A]0 (0.0719 M min1 )(0.90 M )
1
t 12 = 15.45 min
Gas-Phase Reactions
A(g) B(g) + 2C(g)
A B C
PT OT AL = PA + PB + PC
t=0 PA,0 0 0
C -x +x +2x = PA,0 x + x + 2x
t PA,0 -x x 2x = PA,0 + 2x 2
[A]t
n=1 ln = kt
[A]0
P
from PV = nRT, P = MRT, C =
RT
Therefore,
PA,t
RT
ln PA,0
= kt
RT
PA,t
ln = kt
PA,0
Example:
PA,t
ln = (0.0087 min1 )(600 min)
800 mmHg
min1 )(600 min)
PA,t = (e(0.0087 )(800 mmHg) = 4.43 mmHg
PT OT AL = 4.43 + 2x + x
PT OT AL = 4.43 + 2(795.57) + 795.57 = 2391.14 mmHg
Ea
ln k = ln A + ln e RT
Ea 1
ln k =
+
ln A Ea 1
R T ln k2 = R T2 + ln A
y b Ea 1
mx ln k1 = R T1 + ln A
1 ln kk21 = Ea
R T12 T11
Plot ln k vs
T y2 y1 = m(x2 x1 )
Ea
slope =
R
y-int = ln A
Example:
T ( C) 0 25 35 45
k(s1 ) 103 0.0106 0.319 0.986 2.92
Find Ea and A:
Ea 1 1
ln k = + ln A Plot ln k vs r = 0.999
R T T
Ea y int = ln A = 28.336
slope = = 10863
R A = 2.02 1012
E a = 90319 J
1
Find half-life at 40 C: x = y = ln k
T
ln 2
1 t 12 =
ln k = y k
313.15 ln 2
ln k = 6.355 =
1.738 103 s1
k = 1.738 103 s1 = 399 s
Given: n=2
Ea = 250 kJ/mol [N2 O]t = 0.20[N2 O]0 = 0.002 M [N2 O]0 = 0.01 M
T1 = 838.15 K t 12 = 25.25 hours k1 =?
T2 = 973.15 K t =? k2 =?
1 1 1
= kt + t 12 =
[N2 O]t [N2 O]0 k1 [N2 O]0
1 1
k1 = = = 3.96 M 1 hr1
(t 12 )([N2 O]0 ) (25.25 hours)(0.01 M )
k2 Ea 1 1
ln =
k1 R T2 T1
k2 250000 J/mol 1 1
ln = J
3.96 M 1 hr1 8.314 molK 973.15 838.15
k2
= 145.03
3.96 M 1 hr1
k2 = 574.32 M 1 hr1
1 1
= kt +
[N2 O]t [N2 O]0
1 1
= (574.32 M 1 hr1 )t +
0.002 M 0.01 M
t = 0.696 hrs or 41.79 min
5. Catalyst
- substance that is not consumed in the reaction
- alters the activation energy
1. positive catalyst: speeds up the reaction by lowering the activation energy
2. negative catalyst: inhibitor: slows down the reaction by increasing the
activation energy
Reaction Mechanisms
- detailed description of how a reaction occurs
- shows the reason why the observed rate orders are different from the coefficient in the
balanced equation
Rate = k1 [N O2 ]2
Concerted Reaction:
CH3 Cl + OH CH3 OH + Cl
Rate = k[CH3 Cl][OH ]
- you can never tell with absolute certainty the exact mechanism of a reaction, you can
only propose plausible mechanisms
Example 1:
Overall Reaction: 2NO + Cl2 2NOCl Rate = k[NO]2 [Cl2 ]
Mechanism 1
k1
NO + Cl2 NOCl2 (slow)
k2
NO + NOCl2 2NOCl (fast)
2NO + Cl2 2NOCl
N O + Cl2 N OCl2
[N OCl2 ]
K= [N OCl2 ] = K[N O][Cl2 ]
[N O][Cl2 ]
k2 k1 [N O]2 [Cl2 ]
Rate =
k1 + k2 [N O]
If k1 >>> k2 k1 + k2 [N O] k1
k2 k1 [N O]2 [Cl2 ] k2 k 1
Rate = = [N O]2 [Cl2 ]
k1 k1
Holds with experimental rate law
If k2 >>> k1 k1 + k2 [N O] k2 [N O]
k2 k1 [N O]2 [Cl2 ]
Rate = = k1 [N O][Cl2 ]
k2 [N O]
Does not hold with experimental rate law
This means that rate2 < rate1
Example 2:
Overall Reaction: A + 2B C Rate = k[A]2 [B]
A+A A2 (fast)
A2 + B AB + A (slow)
AB + B C (fast)
A + 2B C
Rate = k2 [A2 ][B]
Rate = k2 [B]K[A]2
Rate = k2 K[A]2 [B]
The proposed mechanism is plausible
k2 k1 [A]2 [B]
Rate =
k1 + k2 [B]
If k1 >>> k2 k1 + k2 [B] k1
k2 k1 [A]2 [B] k 2 k1 2
Rate = = [A] [B]
k1 k1
Holds with experimental rate law
If k2 >>> k1 k1 + k2 [B] k2 [B]
k2 k1 [A]2 [B]
Rate = = k1 [A]2
k2 [B]
Does not hold with experimental rate law
This means that rate2 < rate1
Example:
H2 + Br2 2HBr
H2 +Br2 2HBr
Equilibrium Method:
[HOCl][OH ] K[OCl ]
K= [HOCl] =
[OCl ] [OH ]
k2 k1
If k1 >>> k2 , Rate = [I ][OCl ][OH ]1
k1
If k2 >>> k1 , Rate = k1 [OCl ]
Nuclear Chemistry
Chemical Reactions Nuclear Reactions
transformation of the nu-
Change that occurs formation/breaking of bonds
cleus itself
Subatomic Particles Involved valence electrons all subatomic particles
Energy change lower higher
Stability
- atoms with low atomic number: n/p ratio is 1:1
- atomic numbers have higher p-p repulsion so
they need more neutrons to overcome
that repulsion
- atoms without 1:1 ratio are unstable and outside
the belt of stability
- largest atom with a 1:1 ratio is 83Bi
b. Beta Decay: done by nuclei with high n/p ratio p, n, n\p ratio
0 0
Beta Particle: 1 e or 1
234 234 0 1 1 0
Example: 90 U 91 P a +1 e 0 n 1 p +1 e
- the above three decays are ionizing radiation and are harmful
Material Alpha passes? Beta passes? Gamma passes?
Paper NO YES YES
Wood NO NO YES
Concrete/Lead NO NO SOME
- differences are due to different masses and charges of ionizing radiation
Nt
ln = kt
N0
Nt = ekt (N0 )
hr 1 )(48 hrs)
Nt = e(0.0542 (1.50 mg) = 0.111 mg = 1.11 104 g
Mass Defect
- calculated mass of nucleons in a nucleus is always greater than the actual mass
- the mass is transformed into nuclear binding energy
- energy that is released when nucleons combine
- energy that is required to separate the nucleons
- also a measure of stability of a nucleus
- NBE Stability; the nucleus is more intact
Example
28
14 Si atomic mass = 27.96924
1.00728 amu 1.00867 amu
atomic mass = 14 protons + 14 neutrons = 28.22330 amu
proton neutron
m = calculated mass - actual mass = 28.22330 amu 27.96294 amu
m = 0.25406 amu
E = mc2
1g 1 kg
E = (0.25406 amu)(3 108 )2 = 3.798 1011 J
6.02 1023 amu 1000 g
3.798 1011 J
nuclear binding energy per nucleon = = 1.357 1012 J/nucleon
28 nucleons
18 | Chemistry 18: Fundamentals of General Chemistry II
Quiz
ln 2
t 12 =
k
ln 2 ln 2
t 12 = = = 43.5 hours
k 0.159 hr1
Nt
N96 : ln = (0.159 hr1 )(96 hours) = 1.5624
N0
Nt
= 0.2166 remaining 78.34% disintegrated
N0
56
26 F e atomic mass = 55.92066
1.00728 amu 1.00867 amu
atomic mass = 26 protons + 30 neutrons = 56.44938 amu
proton neutron
m = calculated mass - actual mass = 56.44938 amu 55.92066 amu
m = 0.52872 amu
E = mc2
1g 1 kg
E = (0.52872 amu)(3 108 )2 = 7.904 1011 J
6.02 1023 amu 1000 g
7.904 1011 J
nuclear binding energy per nucleon = = 1.41 1012 J/nucleon
56 nucleons
Transuranium Elements
- man-made elements, prepared from Uranium
- located after Uranium in the periodic table
238 239
Example: 1st Transuranium element to be discovered: 92 U (n, ) 93 N p
238 1 239 0
92 U +0 n 93 N p +1 e
411 H + 201 e 4
2 He
Example
1 Ci 3.7 1010 Bq
Activity in Bq = 90 mCi = 3.3 109 Bq
1000 mCi 1 Ci
3.3109 disintegrations 9.121013 J
1 s (7200 s) 1disintegration (0.85)
Absorbed Dose = = 0.246 Gy
75 kg
100 rad
0.246 Gy = 24.6 rad
1 Gy
Absorbed Dose = Gy x RBE = 0.246Gy 1 = 0.246 Sv
100 rem 1000 mrem
0.246 Sv = 24600 mrem
1 Sv 1 rem
Chemical Thermodynamics
- branch of chemistry that deals with heat/energy changes
- predicts the spontaneity of a reaction
Types of System
1. Open - allows the exchange of matter and energy
- nonconservative system
- the wall is permeable and diathermal; imaginary wall
3. Isolated - does not allow the exchange of both matter and energy
- conservative system
- the wall is impermeable and adiabatic; real wall
20 | Chemistry 18: Fundamentals of General Chemistry II
Properties of the System
1. Extensive - properties that are dependent on the amount of matter present
Examples: mass, weight, volume, moles
2. Intensive - properties that are independent on the amount of matter present
Examples: temperature, density, molar mass, boiling point
Extensive Property 1
Intensive Property =
Extensive Property 2
Nonstate Function
- properties that are dependent on the path taken by the system
Examples: q and w
Example: travelling from QC to UPM paths: jeep, FX, taxi distance is constant
distance is the state function fare is the nonstate function
Sign Conventions
(+) q = heat is absorbed by the system (-) q = heat is released by the system
(+) w = work is done on the system (-) w = work is done by the system
- this is because gases are greatly affected by pressure changes and are compressible
- liquids and solids are incompressible and therefore their CV and CP are very close
monoatomic diatomic
3 5
CV R R
2 2
5 7
CP R R
2 2
C P = CV + R
Geoffrey C. Li Notes by A-Log | 21
Work, w (+) w = work is done on the system
(-) w = work is done by the system
F
P-V work: P = F = PA A: cross-sectional area
w = F dx A
A dx = dV P: external pressure
w = P dV Following the sign convention: w = P dV = F dx = P dV
- the negative sign is added to follow direction, it has no bearing on the magnitude
Irreversible Work
Single-Step: from V1 to V2 in one pressure change
Two-Step: from V1 to V2 in two pressure changes
Three-Step: from V1 to V2 in three pressure changes
and so on....
Reversible Work
Infinite Steps: from V1 to V2 in infinite pressure changes
Work in One-Step < Work in Two-Step < Work in Three-Step < < Work in Infinite-Step
Reversible Work - maximum work that the system can perform during expansion
- minimum work that the system can perform during compression
- gradual expansion, infinitesimal change, infinite time is required
wrev = Pgas dV
- therefore, can be easily reversible by also applying
infinitesimal pressure compared to irreversible work
U = q + w
qP = nCP T U = q + w
= nCP T nRT
wirrev = Pext dV
= n(CP R)T
V2 = nCV T
wrev = Pgas dV = Pgas dV
V1
= P V = nRT
2. Isocoric (Constant Volume)
qV = nCV T U = q + w
wirrev = 0 =q
wrev = 0 = nCV T
4. Adiabatic
q=0
U = q + w
U = w
U = nCV T
Example
Given:
Helium Gas n = 3 moles Tf = 100 K Ti = 25 K
wrev =? q=? U=? Assume He is an ideal gas
A: at constant P
qP = nCP T
5 J
qP = (3 mol) 8.314 (100K 25K)
2 molK
qP = 4676.63 J
V2 U = q + w
wrev = Pgas dV
U = 4676.63 J + 1870.65 J
V1
U = 2805.98 J
V2
wrev = Pgas dV = P V = nRT
U = nCV T
V1
3 J
J U = (3 moles) 8.314 (75K)
wrev = (3 moles) 8.314 (75K) 2 molK
molK
wrev = 1870 J U = 2805.98 J
B: at constant V
wrev = 0 U = q + w
qV = nCV T U = q + 0 = q
U = 2805.98 J
3 J
qV = (3 mol) 8.314 (100K 25K)
2 molK
qV = 2805.98 J
U = qp + w Isocoric: H = U + (P V )
U = H + w = nCV T + nRT
H = U w = n(CV + R)T
H = U (P V ) = nCP T
H = U + P V
Isothermal: H = 0
H: enthalpy = U + P V
Adiabatic: H = nCP T
For Ideal Gases: H = nCP T
Example:
Given:
N2(g) n = 2 moles Vf = 4L Vi = 2L
Assume N2(g) is ideal T = 303.15 K
A: reversible
H = 0 U = 0 (isothermal system)
V2 V2
nRT
wrev = Pgas dV = dV
V
V1 V1
V2
dV V2
wrev = nRT = nRT ln
V V1
V1
J 4L
wrev = (2moles)(8.314 )(303.15K) ln
molK 2L
wrev = 3494 J
q = w
q = 3494 J
q = w
q = 405.26 J
Quiz
Given:
O2(g) n = 2 moles T1 = 313.15 K
adiabatic (q=0) Pgas = 4.50 atm Pext = 800 torr
V2 V2
wirrev = Pext dV = Pext dV
nRT
V1 V1 V1 =
P
wirrev = Pext (V2 V1 ) Latm
2 mol 0.08206 molK 313.15K
1 atm V1 =
wirrev = 800 torr (34.26L 11.42L) 4.50 atm
760 torr V1 = 11.42L
J
8.314 molK
wirrev = 24.04 Latm Latm
= 2435.85 J
0.08206 molK V = 3V = 3(11.42L)
2 1
V2 = 34.26L
U = q + w = 0 + w = w
U = 2435.85 J
U = nCV T
5 J
2435.85 J = (2 mol) 8.314 (T2 313.15 K)
2 molK
T2 = 254.55 K
Thermochemistry
- measurement and calculation of heats of reaction at constant pressure
- H is measured
endothermic: H > 0
H = qP H = U + PV H = U + (P V )
exothermic: H < 0
Hrxn = Urxn + ng RT
ng = moles of gaseous products - moles of gaseous reactants
Example
Given:
U = -2648 kJ/mol T = 298.15 K 13 5
13 ng = 4 =
C4 H10(l) + O2(g) 4CO2(g) + 5H2 O(l) 2 2
2
Hrxn = Urxn + ng RT
kJ 5 J 1 kJ
Hrxn = 2648 + 8.314 (298.15 K)
mol 2 molK 1000 J
kJ
Hrxn = 2654.20
mol
qtotal = 0
qrxn + qcal = 0 (dependent on system)
qcal = mcT
= Ccal T (m and c are constant - Ccal : Calorimeter Constant)
Finding Ccal :
qhot H2 O + qtap H2 O + qcal = 0
Finding qf us of ice:
qf us + qice H2 O + qtap H2 O + qcal = 0
Finding qneutralization :
qneut + qacid + qbase + qcal = 0
Example:
Given:
Phenol (C6 H5 OH(s) ) m = 1.800 g Ccal = 11.66 kJ/ C
Bomb Calorimeter T1 = 21.36 C T2 = 26.37 C
qtotal = 0
qcombustion + qcal = 0
qcombustion = qcal = Ccal T
qcombustion = qV = 58.42 kJ per 1.8 g phenol
58.42 kJ 94.12 g
U =
1.8 g 1 mol
kJ
U = 3054.72
mol
kJ J 1 kJ
H = 3054.72 + (1) 8.314 (298.15 K)
mol molK 1000 J
kJ
H = 3057.20
mol
Hf, Br2(g) = 0 (is not a gas in standard state; liquid)
Hf, Cgraphite = 0 (stable allotrope in standard state)
Hf, Cdiamond = 0
Example
13
C4 H10(g) + O2(g) 4CO2(g) + 5H2 O(l)
2
Hrxn = nHf , products nHf , reactants
kJ kJ
= (4 mol) 393.5 + (5 mol) 285.83
mol mol
kJ 13 kJ
(1 mol) 124.73 +( mol) 0
mol 2 mol
= 2878.42kJ
solid liquid Hf us
liquid gas Hvap
solid gas Hsub
Hsub = Hf us + Hvap
Example
kJ
4N H3(g) + 3O2(g) 2N 2(g) + 6H2 O(l) H = 1531
mol
kJ
N2 O(g) + H2(g) N 2(g) + H2 O(g) H = 367.4
mol
1 kJ
H2(g) + O2(g) H2 O(l) H = 285.9
2 mol
4. Bond Enthalpy
- energy required to break 1 mol of a bond
- applicable only to gaseous covalent compounds
- correlated to atomic size and bond length
- bond enthalpy double bond is not equal to twice for that of a single bond
- different nature of bonds (single: sigma, double: sigma + pi)
Example:
13
C4 H10(g) + O2(g) 4CO2(g) + 5H2 O(g)
2
C4 H10(g) + 13
2 O2(g) 4CO2(g) + 5H2 O(g) H = 2630.5 kJ
5H2 O(g) 5H2 O(l) H = 5(44.01 kJ)
C4 H10(g) + 13
2 O2(g) 4CO2(g) + 5H2 O(l) H = 2850.55 kJ
Measuring Hrxn using standard heats of formation is more reliable than using bond enthalp-
ies since bond enthalpies change according to the environment of the bond.
Quiz
Given:
C8 H18 V = 10.00 mL = 0.688 g/mL Ccal = 7.62 kJ/ C
T2 = 66.5 C T1 = 23.2 C Average = 25 C Bomb Calorimeter
329.946 kJ kJ
U = 0.688 g 1 mol = 5467.21 mol
(10.00 mL) 1 mL 114 gC H
8 18
25 25 9
C8 H18(g) +O2(g) 8CO2(g) + 9H2 O(l) ng = 8 =
2 2 2
H = U + ng RT
kJ 9 kJ
= 5467.21 8.314 103 (298.15 K)
mol 2 molK
kJ
= 5478.36
mol
S: entropy
- measure of the degree of disorder or randomness
dqrev
dS =
T
- being an isolated system is important (no exchange between system and surroundings)
- we can treat the whole universe as an isolated system
1. Isobaric 2. Isocoric
3. Isothermal 4. Adiabatic
dqrev dwrev dS = 0
dS = =
T T
(Pgas dV ) Pgas dV
= =
T T
nRT
dV dV
= V = nR
T V
S2 S2
dV
S = nR
V
S1 S1
V2
S = nR ln
V1
qrev Htransition
S = =
T Ttransition
Chemical Reactions
Srxn = nSprod nSreac
Selements = 0
Example
Given:
H2 O(s) H2 O(g) n = 2 moles Tf = 383.15 K Ti = 268.15 K
P = 1 atm
Hf us, ice = 6.02 kJ/mol Hvap, water = 40.67 kJ/mol
ice CP = 37.7 J/molK
liquid water CP = 75.3 J/molK
steam CP = 33.9 J/molK
T2 J 273.15 K
S1 = nCP ln = (2 mol) 37.7 ln
T1 molK 268.15 K
J
= 1.39
K
ST = S1 + S2 + S3 + S4 + S5
J
= 312.22
K
Quiz
Given:
Hf us = 9.87 kJ/mol Hvap = 30.7 kJ/mol Svap = 86.9 J/molK
liquid CP = 136.1 J/molK
gas CP = 84.67 J/molK
Ti = 278.75K
J
Hvap Hvap 30700 mol
Svap = Tb = = J
= 353.28 K
Tb Svap 86.9 molK
ST = S1 + S2 + S3 + S4
J
9870 mol J 353.28 K J J 373.15 K
= + 136.1 ln + 86.9 + 86.67 ln
278.75 K molK 278.75 K molK molK 353.28 K
J
= 159.19
molK
Suniverse > 0
Ssystem + Ssystem >0
qsys
Ssys >0
T
T Ssys qsys >0
at constant P, qP = H T Ssys Hsys >0
Hsys T Ssys <0
Gsys <0
G= H
TS G = H T S
heat available heat used
Example:
Hf us 6.02 kJ/mol
Hf us = 6.02 kJ/mol Sf us = =
Tm 273.15 K
kJ
= 0.02204
molK
G = H T S
kJ kJ kJ
at 0 C : G = 6.02 (273.15K) 0.02204 =0
mol molK mol
EQUILIBRIUM at 0
kJ kJ kJ
at 10 C : G = 6.02 (283.15K) 0.02204 = 0.2204
mol molK mol
SPONTANEOUS at 10
kJ kJ kJ
at -10 C : G = 6.02 (263.15K) 0.02204 = 0.2204
mol molK mol
NONSPONTANEOUS at -10
G = H T S
= [nHf , products nHf , reactants] T [nS , products nS , reactants]
kJ kJ kJ kJ
= (1) 1273.02 + (6) 0 (6) 393.5 + (6) 285.83
mol mol mol mol
J J J J
(288.15 K) (1) 212.1 + (6) 205.0 (6) 213.6 + (6) 69.91
molK molK molK molK
kJ
1000J
= 2880.17 kJ, N ON SP ON T AN EOU S
G = H - T S
+ Reaction is spontaneous at all T
Reaction is spontaneous at low T
+ + Reaction is spontaneous at high T
+ Reaction is nonspontaneous at all T
Gf, elements =0
0K 298.15K
S = S298.15K S0K
S = S298.15K
Chemical Equilibrium
- the moment where there is no change in the concentration of reactants/products
- the reaction is still occurring (dynamic state)
Approaches to Equilibrium
Kinetic Approach
1
N2(g) + O2(g) N O2(g)
2
Thermodynamic Approach
- natural direction of reactions is toward equilibrium
- equilibrium: maximum entropy of the universe. lowest G of the system
- when G = 0, it has achieved the above conditions
1
N2(g) + O2(g) N O2(g)
2
G = G + RT ln Qa Q: reaction quotient
aN O 2 aN O 2
G = G + RT ln 1 Qa = 1
aN2 2 aO2 aN2 2 aO2
at equilibrium:
G = 0
0 = G + RT ln Ka
G = RT ln Ka
G
ln Ka =
RT
G
aN O2
Ka = 1
aN2 2 aO2
PN O2 N O2 PN O2
Ka = 1 = 1 1
(PN2 ) PO22 N2 O2
2 PN2 2 PO2
Ka = K KP
CRTN O2 CN O 2 1
KP = 1 = 1 (RT ) 2
CRTN2 CRTO2 2 CN2 CO22
ng
KP = KC (RT )
Example
kJ 1
Gf,N O2(g) = 51.84 T = 298.15K N2(g) + O2(g) N O2(g)
mol 2
G
K a = e RT
51.84 kJ
=e (8.314103 kJ/molK)(298.15 K)
= 8.27 1010
KP = KC (RT )ng
KP 8.27 1010
KC = n
= 1
(RT ) g [(8.314 103 kJ/molK)(298.15 K)] 2
= 4.09 109
Manipulating Equations
1
N2(g) + O2(g) N O2(g) KP = 8.27 1010
2
1
2 N2(g) + O2(g) N O2(g) KP = (8.27 1010 )2
2
1 1 1
N2(g) + O2(g) N O2(g) KP = (8.27 1010 ) 2
2 2
1
1 N2(g) + O2(g) N O2(g) KP = (8.27 1010 )1
2
Adding/Subtracting
1
2 N2(g)
+ O2(g) O2(g) KC1
N O(g) 1 1
2 N2(g) + 2 O2(g) KC2
N O(g) + 12 O2(g) N O2(g) KC1 KC2
Quiz
2N O(g) N2(g) + O2(g) KP = 1 1030
3
3N O(g) + Br2(g) 3N OBr(g) KP = 715.5
2
1 1
[2N O(g) N2(g) + O2(g) ] (KP = 1 1030 ) 2
2
1 3 1
[3N O(g) + Br2(g) 3N OBr(g) ] (KP = 715.5) 3
3 2
1 1 1
Overall: N2(g) + O2(g) + Br2(g) N OBr(g) KP = 8.944 1015
2 2 2
G = RT ln Ka Ka KP
kJ
= (8.314 103 kJ/molK)(298.15 K)(ln 8.944 105 ) = 91.05
mol
Molecular Equilibrium
Solving Equilibrium Problems
1. Write the balanced equilibrium equation
Homogenous Equilibria
1. Given:
1 mol SO3(g) 2L vessel 303.15 K 12.5% decomposed at equilibrium
[SO2 ]2 [O2 ]
KC =
[SO3 ]2
(0.0625M )2 (0.03125M )
KC =
(0.4375M )2
KC = 6.38 104
ng 4 Latm
KP = KC (RT ) = 6.38 10 0.08206 (303.15 K)
molK
KP = 0.0159
2. Given:
PN O = 300 mmHg PCl = 250 mmHg Peq = 420 mmHg T = 473.15 K
PN OCl
KP = 1
PN O PCL
2
2
260/760
KP = 1
(140/760)(120/760) 2
KP = 16.36
KP 16.36
KC = n
= 1
(RT ) g Latm
0.08206 molK (473.15 K) 2
KC = 101.94
2NH3 N2 + 3H2
I (mol) 0.4 0 0
C (mol) -0.1 +0.05 +0.15
E (mol) 0.30 0.05 0.15
mT OT AL = 0.5 mol
QUIZ
Given: Initial: 0.112 mol O2 0.0400 mol N2 O in 2.00L Equilibrium: 0.0400 mol NO2
Heterogenous Equilibria
[H2 ]
F e(s) + H2 O(l) F eO(s) + H2(g) KC = [H2 O]
2Ag(s) + 12 O2(g) Ag2 O(s) KP = PO
1
0.5
2
[CO]2
C(s) + CO2(g) 2CO(g) KC = [CO2 ]
PT = 450 mmHg = 2x
x = 225 mmHg
2
225
KP = PN H3 PHCl = = 0.0876
760
KP 0.0876
KC = n
= = 1.46 104
(RT ) g [(0.09206)(298.15)]2
1. Concentration
- changes in concentration of solids and pure liquids do not affect equilibrium
3. Temperature
- alters the value of the rate constant
4. Catalyst
- no shift in equilibrium, they affect both the forward and backward reactions
Quantitative Approach
Temperature: alters K
G = RT ln Ka
G H T S
ln Ka = =
RT RT
H 1 S
ln Ka = + (vant Hoff equation)
R T R
1
Plot lnKa vs
T
slope: Endothermic: - Exothermic: +
S
y-int:
R
Two-point form:
Ka2 H 1 1
ln =
Ka1 R T2 T1
Ionic Equilibria
Nonelectrolyte - does not conduct electricity
- does not dissociate into ions
- molecular
Examples: organic molecules C6H12O6, C12H22O11, CO(NH)2
Electrolyte - solutions that conduct electricity (salts, acids, bases)
- dissociates into ions
Strong Electrolyte - strongly conducts electricity
- completely dissociates into ions
Examples: HCl (strong acid), NaOH (strong base), NaCl (salt)
Weak Electrolyte - partially dissociates into ions
- forms coordinate covalent bonds (only one atom donates the electron pair)
- not all Lewis acids are Bronsted-Lowry acids
- other species besides H+ can accept electron pairs
Example: central atoms in complexes
Acid Strength
- capacity to donate the proton (based from the Bronsted-Lowry theory)
From left to right, atomic size increases negligibly, so polarity is more prioritized.
Basicity
Acidity, Basicity
- the stronger the acid, the weaker is its conjugate base.
Examples:
Acidity: HF < HCl < HBr < HI Basicity: F- > Cl- > Br- > I-
Acidity: HNO3 > HNO2 Basicity: NO3- < NO2-
Acidity: NH3 < H2O < HF Basicity: N3- > O2- > F-
Ionization of Water
- water is amphoteric, so it can autoionize (Endothermic Reaction)
Weak Electrolytes
Polyprotic Acids
Salts
- product of the neutralization of an acid with a base
- the cation is from the base and the anion is from the acid
Example: NaCl Na from NaOH; Cl from HCl
More Examples:
[HA][OH ] [H3 O+ ]
Kb =
[A ] [H3 O+ ]
[HA]
Kb = [OH][H3 O+ ]
[A ][H3 O+ ]
1
Kb = KW
Ka
Ka Kb = Kw (for conjugate acid-base pairs)
- this also explains why when an acid is very strong, its conjugate base is weak
Example: NH4F
+
N H4(aq) F(aq)
from a weak base from a weak acid
+
N H4(aq) + H2 O(l) H3 O(aq)
+
+ N H3(aq) (Ka )
F(aq) + H2 O(l) HF(aq) + OH(aq)
(Kb )
Amphoteric Compounds
N aHCO3 N a+
(aq) + HCO3(aq) HCO3 is amphoteric
HCO3(aq) + H2 O(l) H3 O(aq)
+ 2
+ CO3(aq) Ka2 = 5.6 1011
HCO3(aq) + H2 O(l) H2 CO3(aq) + OH(aq)
KW
Kb = K a1
= 2.33 108
Kb is larger, so HCO3 is more basic than acidic
% ionization pH
0.10 M HCl 100% 1.0
0.10 M HCl + 0.05 M NaCl 100% 1.0
0.10 M HOAc 1.34% 2.87
0.10 M HOAc + 0.05 M NaOAc 0.036% 4.44
Weak Bases lower ionization lower pH
Buffer Solutions
- solutions that resist drastic changes in pH upon addition of small amount of acid or base
- because buffers have acids and bases that can neutralize that addition
- biological samples are very sensitive to pH so they need to have buffers
- buffers have ranges in pH that they are effective at (1.0 pH)
- composed of a weak acid/base and its conjugate
[BH + ]
pOH = pKb + log
[B]
- you can form a buffer by neutralizing the acid alone, thus forming a conjugate base (like in
titration)
Acid-Base Indicators
- weak organic acids and weak organic bases that are sensitive to pH changes
The acid formed has a different color than the base formed.
pH range
[In ]
[HIn] 10 base color predominates +1
pKa
[HIn]
10 acid color predominates -1
[In ]
- since formation constants are very large, complex ion formation is very favorable
KSP = [P b2+ ][I ]2 = 1.4 108 KSP = [Al3+ ][OH ]3 = 1.8 1033
Ksp = solubility product constant
- solubility product constants are very small, therefore, the salts are very sparingly soluble
- you cannot say which is more soluble by looking at the Ksp unless they have the same
formula type
5. pH
- only affects salts with basic anions (conjugate bases of weak acids)
- larger amount of basic anions (higher pH) shifts equilibrium backwards
- precipitate forms
- larger amount of acidic anions, (lower pH) neutralizes basic anions
- equilibrium shifts forward, precipitate dissolves
Exceptions:
CuS CdS PbS NiS FeS ZnS
Ksp 6 1037 8 1028 3 1028 3 1020 6 1019 2 1025
- for CuS, CdS and PbS, an increase in pH doesn't increase their solubility
-since their Ksp are low, the removal of the basic anion doesn't cause a large shift forward
Precipitation
P bI2(s) P b2+
(aq) + 2I(aq)
Fractional Precipitation
- precipitation of different compounds in a specific order
- you cannot compare by looking at the Ksp unless they have the same formula type and
concentration.
- if the above is true, then the compound with the lowest Ksp forms first
Dissolution
1. Variation in Temperature
- no significant effect on most salts because of their low Ksp
2. Variation in pH
- only applicable to salts with basic anions
BaCO3(s) Ba2+ 2
(aq) + CO3(aq)
2
CO3(aq) +
+ H3 O(aq) HCO3(aq)
+ H2 O(l)
Amphoteric Hydroxides
- soluble on both acids and bases
+
Al(OH)3(s) + 3H3 O(aq) Al(aq)
3+
+ 6H2 O(l)
Al(OH)3(s) + OH(aq) Al(OH)
4(aq)
+
Zn(OH)2(s) + 3H3 O(aq) Zn2+
(aq) + 4H2 O(l)
Zn(OH)2(s) + 2OH(aq) Zn(OH)2
4(aq)
Electrochemistry
- deals with interconversion of electrical energy and chemical energy
- deals with reduction-oxidation reactions
Electrode potential
- cannot be exactly determined
- measured using a reference electrode
- Standard Hydrogen Electrode (SHE)
+
2H(aq) + 2e H2(g) E = 0V
- electrode potential arbitrarily assigned as 0
- used platinum (an inert electrode, doesnt react) as the solid electrode
Geoffrey C. Li Notes by A-Log | 47
-covered with platinum to increase surface area for more adsorption of H+
- alternative inert electrode: C(s, graphite)
- paired up different electrodes with the SHE to determine their respective potentials
- convention: E must be written as the REDUCTION potential
- oxidation potential = -E
Example:
Arrange the following in order of:
1. Increasing strength as Oxidizing Agent: Cl2, Br2, Ce4+ Br2 < Cl2 < Ce4+
2. Increasing strength as Reducing Agent: Ni, Mn, Cd Ni < Cd < Mn
3. Decreasing strength as Oxidizing Agent in acidic medium:
Cr2O72-, MnO4-, H2O2 H2O2 > MnO4- > Cr2O72-
4. Decreasing strength as Reducing Agent: Co, Ag, Fe Fe > Co > Ag
Example:
Calculate the standard cell potential of the following:
If Ecell > 0, you may say that the reaction is spontaneous at standard state
- the cell is GALVANIC
If Ecell < 0, you may say that the reaction is nonspontaneous at standard state
- the cell is ELECTROLYTIC
Note: Changing the moles of the reaction doesn't change E, it its intrinsic.
To drive the reaction in number 2, you must apply more than 1.24V electricity
G = G + RT ln Q
nF E = nF E + RT ln Q
RT
E = E ln Q Nernst Equation
nF
J
8.314 molK 298.15 K
at 25 C, E = E C
2.303 log Q
n 96485 mol
0.0592
E = E log Q (at 25 C)
n
Applications
1. Determination of Equilibrium Constant
G = RT ln K
nF E = RT ln K
nF E
ln K =
RT
nF E nE
K=e RT K = 10 0.0592 at 25 C
Example:
1. P b(s) + 2CO3+ P b2+ + 2Co2+ Find K
Ecell = Ecathode Eanode = 1.82V (0.13V ) = 1.95V
nE 21.95V
K = 10 0.0592 = 10 0.0592 = 7.56 1065
nE 22.37V
K = 10 0.0592 = 10 0.0592 = 1.17 1080
since K is very very large, the reaction is complete
nE 10.58V
Ksp = 10 0.0592 = 10 0.0592 = 1.59 1010
Quiz
P t|F e3+ (1.20M ), F e2+ (0.0075M )||M nO4 (0.0020M ), H + , M n2+ (2.50M )|P t
Concentration Cell
electrode: determines concentration or activity
reference electrode: potential does not vary with the concentration of the analyte
- independent, fixed potential
Example: SCE - standard calomel electrode (Hg2Cl2)
indicator electrode: sensitive to concentrations of analyte
- potential varies with concentration of analyte
pH meter: reference electrodes: SCE, Ag|Ag+
indicator electrode:
- glass tipped with solution of known pH
- E is generated from difference in potentials between electrode and
surroundings
- calibration: using buffers, constant pH of 4/7/10
- setting what concentration will be pH 4/7/10
50 | Chemistry 18: Fundamentals of General Chemistry II
- checking the proper slope
- in order to find the relationship of potential and pH
For SHE: Ecell = 0.0592pH
Electrolytic Cells
Types of electrical Conduction
1. Electronic Conduction (Metallic Conduction)
- the metal is the conductor because of a large sea of electrons
2, Electrolytic Conduction
- electrolytes are conductors - presence of ions
Mechanism of Electrolysis
1. Migration of Ions towards the electrodes
- Cations to Cathode - Anions to Anode
2. Reaction occurs at the electrodes
- Cathode: Reduction - Anode: Oxidation
Example: electrolysis of molten CaCl2 between Pt electrodes using 10A current for 5 min
Electrode: Inert Electrolyte: Aqueous
Cathode: Ca2+ + 2e Ca(s)
Anode: 2Cl Cl2(g) + 2e
VAu = SA thickness
SA = 2 r2 + dh
SA = 2 (1.25 cm)2 + (2.5 cm)(0.155 cm) = 11.03 cm2
VAu = 11.03 cm2 0.0025 cm = 0.0276 cc
19.3 g
WAu = 0.0276 cc = 0.533 g
cc
Au(CN )
4 + 3e Au(s) + 4CN
10
1 mol 3 mol e 96485 C s
0.533 g = 8703 s = 145.05 min
196.97 g 1 mol mol e 0.100 C 9
Coordination Chemistry
- study of coordination compounds
History
- started with CoCl36NH3, fascinated scientists
- Alfred Werner
Coordination Number: number of donor atoms that surround the central atom
First Coordination Sphere: composed of the central atom and its attached ligands
Example: [Ag(NH3)2]+
Conductivity
Note: Only Complexes with Coordination Numbers 2, 4 and 6 will be studied for Chem 18
Shapes of Complexes
Coordination Number Shape
2 Linear
4 Tetrahedral or Square Planar
6 Octahedral
Example: [PtCl5(NH3)] coordination number: 6 shape: octahedral
Ligands
- denticity: number of donor atoms available
monodentate: one donor atom
Examples: H2O, NH3, Cl-, Br-, I-, F-, CN-, CO (C donates), SCN- OH-
bidentate: 2 donor atoms
- glycinate
polydentate: EDTA: 6 donors: 4 O, 2 N
54 | Chemistry 18: Fundamentals of General Chemistry II
Biological Complexes:
hemoglobin: central atom: Fe ligands: heme, globin, oxygen
Nomenclature of Complexes
1. Cation is named first before the anion
2. In complex parts, ligands are named first before the metal
a. alphabetical order (not including greek prefixes)
b. Greek prefixes to specify number of a ligand
- di, tri, tetra, penta, etc.
- if the ligand already contains a greek prefix, use bis, tris, tetrakis, pentakis and
enclose the ligand it describes in a parenthesis
Ag(NH3)2+ diamminesilver(I)
[Fe(en)3]3+ tris(ethylenediamine)iron(III)
- if adding a Greek prefix can mean another thing for the ligand, use bis, tris etc.
(CH3NH2)2 bis(methylamine) dimethylamine: (CH3)2NH2
(C2O42-) bis(oxalato) bioxalate: HC2O4-
c. ligands that end with ide o bromide - bromo, cyanide - cyano, chloride - chloro
d. ligands that end with ite ito end with ate ato
carbonate - carbonato ONO- - nitrito
C2O42- - oxalato sulfate - sulfato
nitrate - nitrato
e. neutral ligands: same name
3. If the complex is an anion (has a negative charge), end with the latin name (if any) + -ate
K4[Fe(CN)6] potassium hexacyanoferrate(II)
If the complex is neutral or a cation, end it with the metal's english name
[PtCl(NH3)5]Cl3 pentaamminechloroplatinum(IV) chloride
[Fe(en)3](NO3)3 tris(ethylenediamine)iron(III) nitrate
4. Add the oxidation number in parenthesis after the name of the metal
Formula Writing
1. Write the cation first before the anion
2. For Complexes
a. the metal is written first before the ligands
b. anionic ligands are written first before neutral
c. if many ligands, list in alphabetical order based on the first letter of the symbol,
following first the rules above
Example:
1. tetracarbonylnickel(0) [Ni(CO)4]
2. tetraamminedichlorocobalt(III) chloride [CoCl2(NH3)4]Cl
3. potassium hexacyanoferrate(III) K3[Fe(CN)6]
4. dichlorobis(ethylenediamine)platinum(IV) nitrate [PtCl2(en)2](NO3)2
5. tetraamminechromium(II) hexafluoroferrate(III) [Cr(NH3)4]3[FeF6]2
Isomerism
Isomer: compounds with the same formula but different arrangement of atoms
Structural: different links and bonds
Stereoisomerism: different spatial arrangements
Structural Isomers
1. Ionization Isomers: differs by the exchange of a ligand with an atom or neutral molecule
outside the coordination sphere
[Co(SO4)(NH3)5]Br [CoBr(NH3)5]SO4
Red Color Violet
AgBr(s) + AgNO3 no precipitate
no precipitate + BaCl2 BaSO4(s)
Theories on Bonding
Valence Bonding Theory (Localized Electron Model)
- coordinate covalent bond: overlap of 1 empty orbital and 1 filled orbital
- describes bonding using hybrid orbitals and electron pairs
- overlap of empty metal orbital and filled ligand orbital
Octahedral
1. CoF63- 27
Co: [Ar]4s23d7
Co3+: [Ar]3d6
Co3+ : _ _ _ _ __ __ __ __ __ __ __ __ __
3d 4s 4p 4d
_ _ _ _ hybridization to sp3d2
3d sp3d2
OUTER ORBITAL COMPLEX
2. Co(CN)63- 27
Co: [Ar]4s23d7
Co3+: [Ar]3d6
Co3+ : _ _ _ _ __ __ __ __ __ __ ELECTRON PAIRING
3d 3d 4s 4p
hybridization to d2sp3
3d d2sp3
- if 3d orbitals are used for coordinate covalent bonds, stronger metal-ligand bonds are
formed, energy is needed to pair the electrons of the d orbitals
- enough energy is obtained from bond formation to pair the electrons of the 3d orbitals
Tetrahedral
CoCl42- Co2+: [Ar]3d7
Co2+ : _ _ _ __ __ __ __ __ __ __ __ __
3d 4s 4p 4d
_ _ _ hybridization to sp3
3d sp3
OUTER ORBITAL COMPLEX
Square Planar
Ni(CN)42- Ni2+: [Ar]3d8
Ni2+ : _ _ __ __ __ __ __ ELECTRON PAIRING
3d 3d 4s 4p
hybridization to dsp2
3d dsp2
Types of Interaction
1. Electrostatic attraction between metal ion and ligand
2. Electrostatic repulsion between lone pairs on the ligands and the electrons in the d orbit-
als of the metal
Octahedral
- the orbitals dx^2-y^2 and dz^2 are hit by ligands directly when they approach so they must be
as electron-free as possible
- also, the direct hit causes these two orbitals to have higher energy, so a split occurs
Higher orbitals: x2-y2 and z2 are the eg Lower orbitals xy, yz and xz are the t2g
: crystal field splitting energy
Color
- color is shown because it reflects the color or it absorbs the compliment color
- when a complex absorbs light, its electrons become excited and there is an increase in
energy which is equal to the crystal field splitting energy (). It absorbs an amount of energy
to do so, therefore, you can determine the color absorbed and reflected (its compliment).
hc
= hv =
- the size of crystal field splitting is dependent on the nature of the ligands
- interaction, , wavelength absorbed, splitting
Spectrochemical Series
- list of ligands in order of their abilities to split d orbitals
I < Br < Cl < OH < F < H2 O < CN S < N H3 < en < N O2 < CN < CO
Weak-field ligands Strong-field ligands
Examples:
CoF63- (green) Co(CN)63- (yellow)
(too-high for electrons to reach)
eg
_ _
eg
_ _
t2g t2g
- the crystal field theory accounts for the magnetic properties and color of complexes
__
x2-y2 (directly hit)
__ __ __ (t2g)
__
xy (lobes near ligands)
__ __ __ (eg)
z2 (collar interaction)
__ __
xz yz
_ _ _ (t2g)
(eg)
- for square planar and tetrahedral complexes, the spin is related to the geometry
Square Planar: High Spin Tetrahedral: Low Spin
Examples:
1. [Cr(en)3]3+ Cr3+: [Ar]3d3 2. [Mn(CN)6]3- Mn3+:[Ar]3d4
eg eg
_ _ _ _ _
t2g
t2g
_ _ _ _ _
eg t2g
_ _ _
t2g eg
__
Reactions
1. Labile Complexes: highly reactive
- complexes that undergo rapid ligand exchange reactions
[N i(CN )4 ]2 + 4 CN [N i( CN )4 ]2 + 4CN