Stoichiometry

C 12.000 amu

Mole

N = 6.022 * 10^23 C 12gr

!

1 amu = 1.66054 * 10^-24 g 1 g = 6.022 * 10^23 amu 1 mol = 6.022 * 10^23 particles

Molar Mass
!

n !
# "

% $ $
% # "
#( & ' aq s, l, g"
 molA/
molB

molA MolB
1/MMA * MMB
gA GB

Excess Reagent " ! Limiting Reactant ! !

Yield

*
.. -# , " & #+"

#solvant" #solute"
aq

M
# " #

M = n (moles) / V

Density

)
 d = m/v
# "
# "

Mole Fraction
#
xi = ni/ntot

Dilution
#

M0V0 = MtotVtot

*
* * .. .

- . ". *
* " #273˚ C
#
T(K) = t(c) + 273.2
t (F) = 9/5 t(˚C) + 32

$
1 atm = 760 mmHg (TORR)
1 bar = 10^5 PASCAL
1 PASCAL = 1 N/m^2
1 atm = 101,325 PASCALS

/
 !
P * V = n (moles) * R * T
R
R = 0.08206 L. atm / K. mol

!
" ! $
#

Standard Temperature-Pressure STP

T = 0˚ C = 273.2 K 1P = 1.0 atm

22.42 L STP !

!
P1 = X1 * Ptot
#x1 = n1/ntot" $

Boyle
$
P * V = constant

!
#0.5mv^2"

#Hydration"
#Precipitation"

0
 Electrolytes
# !

# "

"
#

#Spectator Ions"
Net Ionic Reaction # "

Acid & Base

Arrhenius !
+
H

Hydronium Ions (H3O+)

OH-

#Oxy-Acids" 3
+
H
1 1

2
 # "
%

# , "
" # , "
#

Neutralization Reaction
% !

OH- H+
Net Ionic Reaction

pH
! pH

pH = -log[H3O+]

& 5 1 & 1 & pH=7

. 0

Acid-Base Titration

# "
)
%

OH- H+
N = neq/V

N*V (base) = N*V (acid)

)
#pH=7"

4
 Oxidation-Reduction

#Redox" 6

Oxidation State / Number % !

#

"
#

!
* *
.
)
/
3 0
)3 2
) # " 4
3 5
. 7
8

!
!
#Reducing"
#Oxidizing"

Disproportionation

5
 /
# " 0
9

2
4
- +
# " #OH " #H " 5

7
 * : :

: :
# " :

v = - [A]/ t

v = k [A]n [B]m
& m+n 1B & m 1A & n1 &k
aA products
v = k [A]2 1v = k [A]1 1v = k [A]0

t
%

&
0
v = - [A]/ t v = k [A]
k = - [A]/ t
t
[A]t = -kt + [A]0
[A]0 y -k %
&

ln[A]t = -kt + ln[A]0

&
2
v = - [A]/ t v = k [A]
2
k[A] = - [A]/ t
1/[A]t = kt + 1/[A]0

8
 k

t1/2 = 0.693/k

-Ea/RT
k=A

-Ea/RT
A

!
C2H4(g) + H2(g) C2H6(g)

!
O(g) + O3(g) 2O2(g)

# " CFC’s

.
 Equilibrium

H2 + I 2 2HI
# "
# "
%
HI

1 * *

! 1 1
* * * *

# "

! !
!
# "

Law of Mass Action

aA + bB gG + hH
#Equilibrium Constant"
Kc = [G]g[H]h/[A]a[B]b
c "
#
 1 # "

!
# " K
%
g h
Kp = [PG * PH ] / [PAa * PB ] b

P = (n/V)RT
n/V
KP = [G]gRgTg[H]hRhTh / [A]aRaTa[B]bRbTb

n
KP = Kc[RT]
# n n& n

#9 "

!
CaCO3 (s) CaO (s) + CO2 (g)
K = [CO2]

Q - Reaction Quotient

Q>K 1 Q=K
Q<K 1 # "
# "* * ;

Le-Chatelier

# " # $ "

)
 !

% 1 %
# H>0 "
# H<0 "
1%

$ " $ $
1 $ #

$ $
# "$
$

Haber #

N2 + 3H2 2NH3
#=-92kJ"
# "
% 1 %
"
#
$

1
2..

/
 # "
% # "
#Saturation"
"
# . +

S gr. / L
"
#
SALT (s) cCATION (aq) + aANION (aq)

KSP = [ANION]a [CATION]c

#Solubility Product"
S
1 QSP > KSP 1 QSP = KSP
QSP < KSP

Common Ion Effect "

! "
#QSP < KSP "
% %

KSP = 4.0 * 10^-11 10.025M NaF CaF2 !

NaF
+ -
NaF Na + F
0.025M
CaF2
CaF2 (s) Ca2+(aq) + 2F-(aq)
x 2x + 0.025

KSP = x(2x + 0.025)^2 = 4.00 * 10^-11

CaF2 % % " 2x << 0.025

2x + 0.025 0.025 # NaF
0.025x = 4.00 * 10^-11
x = 6.4 * 10^-8

0
 x
(2x/0.025) * 100 < 5%
2x
#2.2 * 10^-4 " % CaF2 x
%

2+

Selective Precipitation

"
#

: I- 2.0 * 10-3 M Pb2+ 11.0 * 10-4 Cu+ !

KSP(PbI2) = 1.4*10^-8; KSP(CuI) = 5.3*10^-12
(I-'
[Pb2+] [I-] = 1.4*10^-8 [I-] = 2.6*10^-3M
[Cu+] [I-] = 5.3*10^-12 [I-] = 3.3*10^-8M

2
 Chemical Bonding

Bond Energy !
! ! !

Bond Length #
! !

1 %

Bond Potential
#10^-12m" picometer

Lewis

# "

Octet Rule
! !
#

Covalent Bond
e #Sharing" %
%

Localized Electron (L.E.) Theory

# "
Bonding Pair
Lone Pair

4
 Bond Order

1# " O2
N2
C2

# "
# "
%

!
"
#

e%

#Skeleton Structure"
O C #Terminal Atom" #Central Atom"
H

Resonance

#O3" !

%
$
B.O. = 3/2 = 1.5 3
#* 0,/ "

5
 Formal Charge

* *

# '

)
# "
# " /

#NO" #PCl5" #BF3 "

Bond Polarity
! "

# "
+ -

Electronegativity
! # #
# "
Pauling # "
0.

! !

7
 #. . 0 "
8 1 .0 8 1

%
1

# "
# "

Lewis !
&

VSEPR Theory

Valence Shell Electron-Pair Repulsion Model

# "e
# "

VSEPR
e
Lone-Lone > Lone-Bond > Bond-Bond

Hybridization

8
 #sp sp2 sp3 "p s s s
p p s
1
# "

Intermolecular Forces
%
: :

Van-der-Waals dipole-dipole

Dispersion Forces; London Forces

#Instantaneous Dipole"
1
1 #Induced Dipole"

/
Hydrogen Bonds (
NH3 HF H 2O
#N F O "

# "

4ºC

).
 % B
%

)
 pH
H+
OH- 1

Bronsted-Lowry !

HA + H2O H3O+ + A-
1A- #conjugate base" HA
H 3O + #conjugate acid" H 2O

Ka = [H3O+] [A-] / [HA]

# "

# "
1

H2O(l) + H2O(l) H3O+(aq) + OH-(aq)

1

H2O(l) H+(aq) + OH-(aq)

# "
+ -
KW = [H ] [OH ]
25°C *
+ - -7
[H ] = [OH ] = 1.0 * 10 M
KW = 1.0 * 10-14 M2

# " [H+] < [OH-] 1 [H+] = [OH-] KW

+ -
[H ] > [OH ] 1

))
 pH
+
pH = -log [H ]
p
pH < 7 1 pH > 7 1pH = 7
. 0 pH
pOH pH
+ - -14 2
KW = [H ] [OH ] = 1.0 * 10 M
+ -
log [H ] + log [OH ] = -14
pH + pOH = 14
" pH pH pH
#
pH
pH

!
triprotic diprotic monoprotic
Oxy-Acid
# H+ " Organic Acid

pH
' (H+' 10^-6 M (OH-' (H+'
pH # " 1*10^-10M HCl (OH-

pH

# K a"

Percent Dissociation !
=([ ]/[ ] ) * 100
M
# "

)/
H+
1
#Ka2 Ka1"
H+

CaO + H2O Ca(OH)2

, 0 pOH pH
pH

# "
+ -
#Base + H2O BH + OH "
+ -
Kb = [BH ] [OH ] / [B]

% !
1#K2O "

# " #Amphoteric"
acid/base properties

OH- H+
H+ H+
e e
- -
BF3 + F BF4

pH

)0
 "
1

KCl K+(aq) + Cl-(aq)

HCl KOH
pH=7.00

NaF Na+(aq) + F-(aq)

F- + H2O HF + OH-

#pH>7.00"
F- HF
# " Ka
# " Kb

Ka Kb = ([F-] [H+] / [HF]) * ([HF] [OH-] / [F-]) = [H+] [OH-] = Kw

Ka Kb = Kw

!
NH4Cl NH4+(aq) -
+ Cl (aq)
#pH<7.00"
NH4+ + H2O NH4OH + H+

NH4CN NH4+(aq) + CN-(aq)

Ka<Kb 1pH<7.00 Ka>Kb

pH=7.00 Ka=Kb 1pH>7.00

)2
 Buffer Solutions
OH- H+ pH !
Buffer Range pH
% ±0.1 1±1
Buffer Capacity pH

# " 3 pH 7
# " 7 pH 10
pH>10 1 pH<3 "
pH #
% pH
# % 1 % "

.+
3 pH 7 !
+ - -5 +
HA H + A Ka=10 [H ] pH
[M]0 0.2 — 0.3
[M]eq 0.2-x x 0.3+x x(0.3+x)/0.2-x 6.6*10^-6 5.18
%
.+ %

# "
" 0.01M
# x
+ - -5 +
HA H + A Ka=10 [H ] pH
[M]0 0.2 +0.01 0.3
0.21 — 0.29
[M] eq 0.21-x x 0.29+x x(0.29+x)/0.21-x 7.2*10^-6 5.14
9 . .0 pH

[H+] "
#
+ - -5 +
HA H + A Ka=10 [H ] pH
[M]0 0.2 -0.01 0.3
0.19 — 0.31
[M] eq 0.19-x x 0.31+x x(0.31+x)/0.19-x 6.1*10^-6 5.21
9 . ./ pH

)4
 Henderson & Hasselbach Equation
pH
+ -
Ka = [H ][A ]/[HA]
[H+] = Ka[HA]/[A-]
-log[H+] = -log Ka[HA]/[A-]
pH = pKa + log[ ]/[ ]

pH

9 /. 5 .. pH 0.05 M HCl

!
B(ase)(aq) + H2O(l) BH+(aq) -
+ OH (aq)

NH3 + H2O NH4+ + OH-

% %
BCl B+(aq) -
+ Cl (aq)
NH4Cl(s) NH4+(aq) + Cl-(aq)
Henderson & Hasselbach
Kb = [BH+][OH-]/[B]
[OH-] = Kb[B]/[BH+]
pOH = pKb + log[ ]/[ ]

pKb = 3.38 pOH PKb Kb = 4.2*10^-4 methylamin

0.5M )
CH3NH3Cl /
pOH = pKb + log[salt]/[acid] pH = 11.02 0.2M 0
0.1<[salt]/[base]<10 pKb
±1
.+ 2
+
[H ] = 0.05
pH = 10.88
. 0 pH

)5
 1

# "
# "

E0 (volts)

25ºC
$ 1 atm
1M
# " E0(v)
E0(v) .
# " # "
1#e "
" # "
#e
# "
E0(v)

" &
# 1
&

E0cell = E0anode + E0cathode

# " # "
Al (s) | Al3+(aq) || Fe2+(aq) | Fe(s)

)7
 # !
# "
E0cell = - E0metal H2 1
0
#Zn, Mg, Al " E
#Cu, Ag " HNO3

E0cell > 0 &

0
E cell <0 &
3+ 2+
:3Cu (s) + 2Al 3Cu + 2Al (s) !
0 3+ 0 0 2+ 0
E (Al Al + 3e) = E cathode = -1.66 1E (Cu Cu + 2e) = E anode = -0.36
0 0 0
E cell =E anode +E cathode = -2.00V<0

W = n F E0cell
& F 1# " n 1J W
-
1F = qe * N = 1.6 * 10^-19 * 6.022 * 10^23 = 96485 C/mole e

Nernst
# "
1

Nernst
Ecell = E0cell - RT/nF lnQ
8.345 J/mol. K. R1 Q
25ºC *
0
Ecell = E cell - 0.0592/n logQ

K E0cell
Ecell = 0
0
E cell = 0.0592/n logK

)8
 # "

#Cu Cu2+ "

#
(i*t)/F * MM/n = m
-
1 e & n 1#e- " & F1 & t1 &i
&m

ANODE 2H2O O2(g) + 4H+ + 4e- E0=-1.23V

CATHODE 4H2O + 4e- 2H2 + 4OH- E0=-0.83V
TOTAL 6H2O 2H2 + O2 + 4(H+ + OH-) E0cell=2.06

2H2O(l) 2H2(aq) + O2(aq)

1
# H 2"
# O 2"

" NaCl
# " NaOH # Na

/.
 1 %
1

!
Joule

)*+,+-

E=q+W

$
$
H<0 H
H>0 1

25ºC * 1.00 atm $

1.00 atm $ 11M

# " Hr

Hf 0
1mole

kJ/mole

/
 H r0 = H f0 ( )- H f 0( )

Hr 0

)
/

. 0

% , %

J/K. mole S

S = S + S

S =- H /T
#"

. ! 0(K)

Sr = S0 ( ) - S0( )

/)
 #
#

G Gibbs !

G= H-T S
H S G = H - 298 S0
0 0
T=298K
G = H0 - T S0

#
G<0
G>0
G=0
S<0 H>0 1# G<0 " S>0 H<0
H, S>0 1
G

G0 f !
1mole

!
G 0r = G f0 ( )- G f 0( )

G0 r

)
/

. 0

//
 !
0
G = G + RT lnQP
R = 8.3145 J/mol. K.

G0 = -RT lnKP
25ºC

G = -nFE

E>0
G<0

/0