Thermochemistry and Concentration Hess’ Law

EQUATION 7: ∆𝐻𝑟𝑥𝑛 = Σ∆𝐻(𝑠𝑡𝑒𝑝𝑠)

Thermochemistry → EXAMPLE
Definition of terms ●
1
𝑁2 + 𝑂2 → 𝑁𝑂2, ∆𝐻 = ?
2
→ U - internal energy
Given:
● EQUATION 1: U = q + w
[1] 𝑁2 + 𝑂2 → 2𝑁𝑂, ∆𝐻 = 118. 5𝑘𝐽
○ q - system/heat
[2] 2𝑁𝑂 + 𝑂2 → 2𝑁𝑂2, ∆𝐻 =− 114. 14𝑘𝑗
■ Negative - system release
■ Positive - system absorbs Solution:
1 1
○ w - work [1] 2
𝑁2 + 2
𝑜2 → 𝑁𝑂, ∆𝐻 = 90. 25𝑘𝐽
■ Negative - done by the system 1
[2] 𝑁𝑂 + 2
𝑂2 → 𝑁𝑂2, ∆𝐻 =− 57. 07𝑘𝐽
■ Positive - done on the system
● EQUATION 2: q(sys) + q(surrounding) = 0
∆𝐻𝑟𝑥𝑛 = 90. 25 + (57. 07) = 33. 18𝑘𝐽
● EQUATION 3: q(sys) = -q(surrounding)
→ EXAMPLE
Enthalpy and Entropy
●
∆𝐻𝑓 - enthalpy of formation
HCl NaOH
→ EQUATION 8:
[] 1.00 1.00 ∆𝐻𝑟𝑥𝑛 = Σ𝑉𝑝∆𝐻𝑓 (𝑝𝑟𝑜𝑑𝑢𝑐𝑡𝑠) − Σ𝑉𝑝∆𝐻𝑓 (𝑟𝑒𝑎𝑐𝑡𝑎𝑛𝑡𝑠)

V 100 mL 100 mL
S - entropy
𝑇𝑖 21.1 21.1 → Criteria for ∆𝐺
● ∆𝐺 < 0 - spontaneous
𝑇𝑓 27.8
● ∆𝐺 > 0 - non-spontaneous
q(reaction) = -q(water) ● ∆𝐺 = 0 - equilibrium
=− (200 𝑚𝐿 ×
1𝑔
)(4. 184
𝐽
)(27. 8 − 21. 1) → ∆𝐺 and ∆𝑆 (EQUATION 9 AND 10)
1 𝑚𝐿 𝑔𝐶
=− 5. 6𝑘𝐽, 𝑒𝑥𝑜𝑡ℎ𝑒𝑟𝑚𝑖𝑐 ● ∆𝑆𝑟𝑥𝑛 = Σ𝑉𝑝∆𝑆𝑓 (𝑝𝑟𝑜𝑑𝑢𝑐𝑡𝑠) − Σ𝑉𝑝∆𝑆𝑓 (𝑟𝑒𝑎𝑐𝑡𝑎𝑛𝑡𝑠)
→ EQUATION 4: 𝑤 =− 𝑃𝑒𝑥𝑡∆𝑇 ● ∆𝐺𝑟𝑥𝑛 = Σ𝑉𝑝∆𝐺𝑓 (𝑝𝑟𝑜𝑑𝑢𝑐𝑡𝑠) − Σ𝑉𝑝∆𝐺 (𝑟𝑒𝑎𝑐𝑡𝑎𝑛𝑡𝑠)
● EXAMPLE: A gas expands, absorbs 25J of heat,
does 243J of work, what is the value of ∆𝑈 EXAMPLE: is the reaction spontaneous under the
∆𝑈 = 𝑞 + 𝑤 following conditions
= 25𝐽 − 243𝐽 =− 218𝐽 ● Given:
→ State functions 2𝑁𝑂 + 𝑂2 → 2𝑁𝑂2 at 298K, 1 atm
● Path independent
∆𝐻 ∆𝐺 ∆𝑆
● At constant V, ∆𝑉 = 0
● EQUATION 5: ∆𝑈 = 𝑞(𝑟𝑥𝑛) + 𝑃∆𝑉 = 𝑞𝑣 𝑁𝑂 90.25 86.55 210.7
→ H - enthalpy
𝑂2 0 0 205.0
● EQUATION 6: ∆𝐻 = ∆𝑈 + 𝑃∆𝑉
○ ∆𝐻 = 𝑞𝑝
𝑁𝑂2 33.18 51.29 240.0
→ EXAMPLE
● In a bomb calorimeter:
𝐶12𝐻22𝑂11+ 12𝑂2 → 11𝐻2𝑂 + 12𝐶𝑂2 Solution:
𝑃∆𝑉 = ∆𝑛𝑔𝑟𝑡 = 0 ∆𝐺 =− 70. 5 𝑘𝐽/𝑚𝑜𝑙
It is spontaneous
 → EXAMPLE: 4𝑁𝐻3 + 5𝑂2 → 4𝑁𝑂 + 6𝐻2𝑂
Reaction Quotient
● Relate the appearance of 𝐻2𝑂 to the
Consider: aA + bB → cC + dD
𝑐 𝑑 disappearance of 𝑁𝐻3
(𝐶) (𝐷)
→ EQUATION 11: 𝑄 = 𝑎 𝑏
(𝐴) (𝐵) ∆[ 𝐻2𝑂] −6∆[ 𝑁𝐻3]
○ Do not include pure solids/liquids ○ ∆𝑡
= 4∆𝑡

∆𝐺 is not standard Reaction rates

→ EQUATION 12: ∆𝐺 =− 𝑅𝑇𝑙𝑛𝑘 → Average rate
→ EQUATION 13: − 𝑅𝑇 𝑙𝑛𝑘 = ∆𝐻 − 𝑇∆𝑆 → Instantaneous rate - rate at a particular instant
−∆𝐻 1 ∆𝑆
→ EQUATION 14: 𝑙𝑛𝑘 = 𝑅
( )+
𝑇 𝑅
→ Initial rate - rate when reacts come into contact
−∆𝐻
● Slope: 𝑅
⇒ ∆𝐻 =− 𝑚𝑟
∆𝑆
Rate law
● Y-intercept: 𝑏 = 𝑅
⇒ ∆𝑠 = 𝑏𝑅 𝑚 𝑛
→ EQUATION 2: 𝑟 = 𝑘[𝐴] [𝐵]
● k - rate constant
When given 2 data points
∆𝐻 1 1 ● m and n - orders
→ EQUATION 15: 𝑙𝑛𝑘1 − 𝑙𝑛𝑘2 = (𝑇 − )
𝑅 1
𝑇2 ○ m + n = overall order
→ Partial pressures
Bond Dissociation Energy
● 𝑃𝑉 = 𝑛𝑅𝑇
EQUATION 16: Bonds broken - bonds formed ○ EQUATION 3: 𝑃 = [ ]𝑅𝑇
■ [ ] - concentration
EXAMPLE: 𝐶𝐻4 + 𝐶𝑙2 → 𝐶𝐻3𝐶𝑙 + 𝐻𝐶𝑙
→ What is the enthalpy of the reaction Method of initial rates (EXAMPLE)
2− −
Given: → 2𝐻𝑔𝐶𝑙2 + 𝐶2𝑂4 → 2𝐶𝑙 + 2𝐶𝑂2 + 𝐻𝑔2𝐶𝑙2
[1] D (C-H) = 414
Given:
[2] D (Cl-Cl) = 243
[3] D (C-Cl) = 339 Exp. 𝐻𝑔𝐶𝑙2 𝐶2𝑂4
2− Rate (r)
[4] D (H-Cl) = 431
1 0.105 0.15 1. 8 × 10
−5

Solution:
2 0.105 0.30 7. 0 × 10
−5
[4(414) + 243] - [3(414) + 339 + 431] = -113
kJ/mol 3 0.052 0.30 −5
3. 5 × 10
Chemical Kinetics ● Find the rate constant and the overall order
𝑚 𝑛 −5
𝑅2 𝑘(0.105) (0.30) 7×10
○ = =
Reaction Rate and Rate Law 𝑅3 𝑚
𝑘(0.052) (0.30)
𝑛
3.5×10
−5

𝑚
Kinetics 2 =2
→ Reaction rate, r m = 1, 1st order, w.r.t 𝐻𝑔𝐶𝑙2
→ Changes in concentration or pressure with respect to 𝑅2
𝑚
𝑘(0.105) (0.30)
𝑛
7×10
−5
○ 𝑅1
= 𝑚 𝑛 = −5
time 𝑘(0.105) (0.15) 1.80×10
𝑛
→ EQUATION 1: aA + bB → cC + dD 2 =4
1∆𝐴 1∆𝐵 1∆𝐶 1∆𝐷 2−
● 𝑟 =− =− = = n = 2, 2nd order, w.r.t 𝐶2𝑂4
𝑎∆𝑡 𝑏∆𝑡 𝑐∆𝑡 𝑑∆𝑡
𝑟
○ Therefore, k = 2− 2
[𝐻𝑔𝐶𝑙2][𝐶2𝑂4 ]
−3 −2 −1
𝑘 = 7. 62 × 10 𝑚 𝑚𝑖𝑛 at specific
T
Orders
Chemical Equilibrium
→ Zero order - m + n + … = 0
● EQUATION 4: 𝑟 = 𝑘
Equilibrium Constant Expression
○ [𝐴]𝑡 =− 𝑘𝑡 + [𝐴]0
Consider: aA + bB → gG + hH
■ [𝐴]0 - initial rate 𝑔 ℎ
(𝑎𝐺) (𝑎𝐻)
○ Negative slope and downward line → EQUATION 1: 𝐾 = 𝑎 𝑏
(𝑎𝐴) (𝑎𝐵)
○ Y-axis - [𝐴]𝑡; X-axis - t ● a = [ ]: aqueous solutions
● EQUATION 5: 𝑡 [𝐴]0
● a = P: gasses
1/2= 2 ● a = 1: pure solids/liquids
○ Half-life for zero order 𝑔
[𝐺] [𝐻]
ℎ
→ EQUATION 2: 𝐾 =
→ First order - m + n + … = 1 𝑐 𝑎
[𝐴] [𝐵]
𝑏

1
● EQUATION 6: 𝑟 = 𝑘[𝐴] ● Equilibrium - rate of the forward = rate of the
○ 𝑙𝑛[𝐴]𝑡 =− 𝑘𝑡 + 𝑙𝑛[𝐴]0 reverse
𝑎 𝑏 𝑔 ℎ
○ Negative slope and downward line ● 𝑘1[𝐴] [𝐵] = 𝑘−1[𝐺] [𝐻]
○ Y-axis - 𝑙𝑛[𝐴]𝑡; X-axis - t → In gaseous forms
𝑔 ℎ
𝑙𝑛 2 (𝑃𝐺) (𝑃𝐻)
● EQUATION 7: 𝑡 = ● 𝐾= 𝑎 𝑏
1/2 𝑘 (𝑃𝐴) (𝑃𝐵)

○ Half-life for first order ● EQUATION 3: 𝐾 = (𝑅𝑇)

∆𝑛𝑔
· 𝐾𝑐
𝑝
→ Second order - m + n + … = 2
2 → EXAMPLES
● EQUATION 8: 𝑟 = 𝑘[𝐴]
● 𝑁𝐴𝐻𝐶𝑂3 decomposes at some T to 𝐶𝑂2.
1 1
○ [𝐴]𝑇
= 𝑘𝑡 + [𝐴]0 Calculate the P𝐶𝑂2 at equilibrium, 𝐾𝑝 = 0. 231
○ Positive slope and upward line 2𝑁𝑎𝐻𝐶𝑂3 ⇔ 𝑁𝑎2𝐶𝑂3 + 𝐶𝑂2 + 𝐻2𝑂
1
○ Y-axis - [𝐴]𝑡
; X-axis - t 𝐾𝑝 = 𝑃𝐻2𝑂 · 𝑃𝐶𝑂2 (1:1 ratio)
1 2
● EQUATION 9: 𝑡 = 𝑘[𝐴]0
𝐾𝑝 = (𝑃𝐶𝑂2)
1/2
0. 231 = 𝑃𝐶𝑂2
Reaction Rate and Rate Law
0. 480𝑎𝑡𝑚 = 𝑃𝐶𝑂2
Theoretical model for kinetics
● A 5L flask is filled with 1.86 mol of NOBr. At eq.
→ Collision theory
and 25 celcius, 0.082 mol of 𝐵𝑟2 is present.
● Sufficient kinetic energy
Calculate 𝐾𝑐 and 𝐾𝑝
● Correct orientation
→ Transition state theory 2𝑁𝑂𝐵𝑟 ⇔ 2𝑁𝑂 + 𝐵𝑟2
● CONSIDER: Reactants → Activated complex →
Products

−𝐸𝑎 1
ARRHENIUS EQUATION: 𝑙𝑛 𝑘 = 𝑅
( 𝑇 ) + 𝑙𝑛 𝐴
→ Negative slope and downward line
→ Having two data points
𝑘2 𝐸𝑎 1 1
→ EQUATION 10: 𝑙𝑛 𝑘 = 𝑅 ( 𝑇 − 𝑇 )
1 2 1
 → EXAMPLE:
A B C
5
● 𝑁2 + 3𝐻2 → 2𝑁𝐻3, 𝐾 = 5. 8 × 10
I 1.86 0 0 1 3
What is K’ for 𝑁𝐻3 ⇔ 2
𝑁2 + 2
𝐻2
C -0.164 +0.1.64 0.082
1
𝐾' = 𝐾
E 1.696/5 1.696/5 1.696/5
○ The equation was reversed
1
[] 0.3392 0.0328 0.0164 ○ The equation was multiplied by 2

1
𝐾' = 5
2 5.8×10
[𝑁𝑂] [𝐵𝑟2] −4
𝐾𝑐 = 2 = 1. 53 × 10 = 1. 8 × 10
−3
[𝑁𝑂𝐵𝑟]
1
𝐾𝑝 = (𝑅𝑇)
∆𝑛𝑔
𝐾𝑐, ∆𝑛𝑔 = 1 ● 𝑁2𝑂 + 2
𝑂2 → 2𝑁𝑂, 𝐾 = ?

−4 Given:
𝐾𝑝 = (0. 08206)(298)(1. 53 × 10 ) 1 −19
𝑁2 + 2
𝑂2 ⇔ 𝑁2𝑂, 𝐾1 = 5. 4 × 10
−3
𝐾𝑝 = 3. 74 × 10 −31
𝑁2 + 𝑂2 ⇔ 2𝑁𝑂, 𝐾2 = 4. 6 × 10
● A 0.0240 mol 𝑁2𝑂4 (g) equilibrates with 𝑁𝑂2 in
a 0.372L flask at 25 celsius. Calculate moles of
Solution:
𝑁2𝑂4 and 𝑁𝑂2 at equilibrium 𝐾2 −31
4.6×10
−3 𝐾= =
𝑁2𝑂4(𝑔) ⇔ 2𝑁𝑂2(𝑔), 𝐾𝑐 = 4. 61 × 10 𝐾1 5.4×10
−19

−13
= 8. 52 × 10
→ Le Chatlier’s principle
A B
● Effect of concentration
I 0.0240 ○ Qc = Kc: equilibrium
○ Qc < Kc: reaction moves forward
C -x +2x
○ Qc > Kc: reaction moves backward
E 0.0240-x 2x ● Effect of volume and pressure
○ ↑V, moves to the left
[] 0.0240−𝑥 2𝑥
0.372 0.372 ■ ↓P
○ ↓V, moves to the right
[𝑁𝑂2]
2 ■ ↑P
−3
𝐾𝑐 = 𝑁2𝑂4
= 4. 61 × 10 ● Effect of temperature
2𝑥 2 2
○ ↑T, moves to the left
−3 ( 0.372 ) 4𝑥
4. 61 × 10 = 0.0240−𝑥 = ○ ↓T, moves to the right
0.372(0.0240−𝑥)
0.372
○ Exothermic reaction favors the reverse
2 −3 −5
4𝑥 + (1. 71 × 10 )𝑥 − 4. 12 × 10 =0 reaction
−3
𝑥 = 3. 00 × 10 ○ Endothermic reaction favors the forward
𝑛(𝑁2𝑂4) = 0. 0210 𝑚𝑜𝑙; reaction
−3
𝑛(𝑁𝑂2) = 6. 00 × 10 𝑚𝑜𝑙
→ Relationship of Kq and the balanced reaction
1
● Reverse reaction: 𝐾
𝑛
● Multiplying the reaction by n: 𝐾
● Combining chemical equations: 𝐾 = 𝐾1 × 𝐾2
→ EXAMPLE → EQUATION 4 & 5:
2+ 2+ + 4+ +
● 2𝐶𝑢 + 𝑆𝑛 ⇔ 2𝐶𝑢 + 𝑆𝑛 , 𝐾𝑐 = 1. 98 ● − 𝑙𝑜𝑔[𝐻 ] = 𝑝𝐻
○ Predict the direction of the reaction ● − 𝑙𝑜𝑔[𝑂𝐻 ] = 𝑝𝑂𝐻
−

when → EXAMPLE
2+ 2+ + 4+ +
[𝐶𝑢 ] = [𝑆𝑛 ] = [𝐶𝑢 ] = [𝑆𝑛 ] = 0. 1 ● A sample has pH = 2.85. Calculate [𝐻 ] and
−
[𝑂𝐻 ]
+ 2 4+
[𝐶𝑢 ] [𝑆𝑛 ] + −𝑝𝐻 −2.85
𝑄𝑐 = 2+ 2 2+
= 1. 00𝑀 < 𝐾𝑐 [𝐻 ] = 10 = 10
[𝐶𝑢 ] [𝑆𝑛 ]
−3
Therefore, reaction moves forward = 1. 41 × 10 𝑀
−3
→ ∆𝐻, ∆𝑆, ∆𝐺, 𝑘, 𝑞 pOH = 14 − 1. 41 × 10
◦ ◦ ◦ − −(14−𝑝𝐻) −12
● EQUATION 4: ∆𝐺 = ∆𝐻 = 𝑇∆𝑆 [𝑂𝐻 ] = 10 = 7. 8 × 10 𝑀
◦
● EQUATION 5: ∆𝐺 = ∆𝐺 + 𝑅𝑇𝑙𝑛𝑄
Acid-Base Systems
◦
● EQUATION 6: ∆𝐺 =− 𝑅𝑇𝑙𝑛𝑘
Strong acids and bases
→ Large Ka and Kb
Acids and Bases → Complete dissociation
→ EXAMPLE
Acid and Bases ● Consider: 0. 015𝑀 𝐻𝐶𝑙, 𝐻𝐶𝑙 → 𝐻 + 𝐶𝑙
+ −

+ − −
Theories Calculate [𝐻 ], [𝑂𝐻 ], [𝐶𝑙 ], pOH, and pH
→ Arrhenius theory +
[𝐻 ] = 0. 015𝑀, [𝐶𝑙 ] = 0. 015𝑀
−

+
● Acid - produces 𝐻 ● Molar ratios are 1:1:1
● Base - produces 𝑂𝐻
− pH = 1.82, pOH = 14 - 1.82
− −12.18
→ Bronsted-Lowry theory [𝑂𝐻 ] = 10
● Acid - proton donor
● Base - proton acceptor Weak acids and bases
● 𝐶𝐻3𝐶𝑂𝑂𝐻 + 𝐻2𝑂 ⇔ 𝐶𝐻3𝐶𝑂𝑂 + 𝐻
+ → Small Ka and Kb
→ Incomplete dissociation
→ Lewis theory
→ EXAMPLE
● Acid - electron acceptor
● Consider: 0. 1𝑀 𝐻𝐶𝑙, 𝑝𝐻 = 1. 00 and
● Base - electron donor
0. 1 𝐻𝑂𝐴𝑐, 𝑝𝐻 = 2. 87
● 𝐵𝐹3 + 𝑁𝐻3 ⇔ 𝐵𝐹3𝑁𝐻3 + − −5
𝐻𝑂𝐴𝑐 ⇔ 𝐻 + 𝑂𝐴𝑐 , 𝐾𝑎 = 1. 8 × 10
Acid-Base Behavior
Ka and Kb A B C
+ −
→ Consider: 𝐻𝑂𝐴𝑐 + 𝐻2𝑂 ⇔ 𝐻2𝑂 + 𝑂𝐴𝑐 I 0.1
+ −
● 𝐻𝑂𝐴𝑐 ⇔ 𝐻 + 𝑂𝐴𝑐
+ −
C -x +x +x
[𝐻 ][𝑂𝐴𝑐 ]
● EQUATION 1: 𝐾𝑎 = −
[𝐻𝑂𝐴𝑐 ] E 0.1 - x x x
−
→ Consider: 𝑁𝐻3 ⇔ 𝑁𝐻4 + 𝑂𝐻
− + −
[𝑂𝐻 ][𝑁𝐻4] −5 [𝐻 ][𝑂𝐴𝑐 ]
● EQUATION 2: 𝐾𝑏 = [𝑁𝐻3]
𝐾𝑎 = 1. 8 × 10 = [𝐻𝑂𝐴𝑐]
2 2
+ − 𝑥 𝑥
→ EQUATION 3: 𝐾𝑤 = [𝐻 ][𝑂𝐻 ] = 0.1−𝑥
= 0.1
−14 −3 +
● 10 at 25 celsius 𝑥 = 0. 1𝐾𝑎 = 1. 34 × 10 = [𝐻 ]
● 14 = pH + pOH pH = 2.87
 +
[𝐻 ]
% ionization = [𝐻𝐴]𝑖
𝑥100 = 1. 342% Buffers
Very minimal is ionized Buffers
→ ↑ dilution = ↑ ionization → Resists change in pH
→ EXAMPLE: What are the base/acid strengths → Combinations of buffers
● ● Weak acid + Conjugate Base
Acid Ka Strength ● Weak base + Conjugate Acid
−
[𝐴 ]
→ EQUATION 6: 𝑝𝐾𝑎 + 𝑙𝑜𝑔( [𝐻𝐴] )
HOAc 1. 8 × 10
−5 3rd
● EQUATION 7: 𝑝𝐾𝑎 =− 𝑙𝑜𝑔 (𝐾𝑎)
𝐻𝐶𝑙𝑂2 1. 1 × 10
−2 1st → EXAMPLES
● In 0.25M HOAc in a 300mL beaker, NaOAc is
HF 6. 6 × 10
−4 2nd added as a buffer. What is its mass?
● Given:
[1] pH = 5.09
Base Kb Strength −5
[2] HOAc Ka = 1. 8 × 10
𝑁𝐻3 1. 8 × 10
−5 1st [3] MW (NaOAc) = 82.0 g/mol

𝐶6𝐻5𝑁𝐻2 −10 3rd

7. 4 × 10 Solution #1:
+ −
[𝐻 ][𝑂𝐴𝑐 ]
𝐶17𝐻19𝑂5𝑁 7. 4 × 10
−7 2nd 𝐾𝑎 = [𝐻𝑂𝐴𝑐]
−5
− 𝐾𝑎 [𝐻𝑂𝐴𝑐] (1.8×10 )(0.25)
[𝑂𝐴𝑐 ] = + = −5.09 = 0. 55𝑀
[𝐻 ] 10
Polyprotic acids 0.55 𝑚𝑜𝑙 82.0𝑔
[𝑁𝑎𝑂𝐴𝑐] = 𝐿
× 0. 3𝐿 × 𝑚𝑜𝑙
= 14𝑔
→ Acids that have multiple protons to donate
+ − −3
→ 𝐻3𝑃𝑂4 ⇔ 𝐻 + 𝐻2𝑃𝑂4 , 𝐾𝑎 = 7. 1 × 10
Solution #2:
− + 2− −8 −
→ 𝐻2𝑃𝑂4 ⇔ 𝐻 + 𝐻𝑃𝑂4 , 𝐾𝑎 = 6. 3 × 10 𝑝𝐻 = 𝑝𝐾𝑎 + 𝑙𝑜𝑔( [𝐻𝐴] )
[𝐴 ]

− + 3− −13
→ 𝐻𝑃𝑂4 ⇔ 𝐻 + 𝑃𝑂4 , 𝐾𝑎 = 4. 2 × 10 −
= 𝑝𝐾𝑎 + 𝑙𝑜𝑔[𝑂𝐴𝑐 ] − 𝑙𝑜𝑔[𝐻𝑂𝐴𝑐]
→ EXAMPLE −
𝑙𝑜𝑔[𝑂𝐴𝑐 ] = 𝑝𝐻 − 𝑝𝐾𝑎 + 𝑙𝑜𝑔[𝐻𝑂𝐴𝑐]
● 3.00M 𝐻3𝑃𝑂4 = 5. 09 − 4. 74 + 𝑙𝑜𝑔(0. 25) =− 0. 25
+ − − −0.25
+ − [𝐻 ][𝐻2𝑃𝑂4 ] [𝑂𝐴𝑐 ] = 10 = 0. 56𝑀
𝐻3𝑃𝑂4 ⇔ 𝐻 + 𝐻2𝑃𝑂4 , 𝐾𝑎 = [𝐻3𝑃𝑂4] 0.55 𝑚𝑜𝑙 82.0𝑔
[𝑁𝑎𝑂𝐴𝑐] = 𝐿
× 0. 3𝐿 × 𝑚𝑜𝑙
= 14𝑔
A B C

I 3M

C -x +x +x

E 3.00 - x x x
2 2
𝑥 𝑥
𝐾𝑎 = 3−𝑥
= 3
+ −
𝑥 = 3𝐾𝑎 = 0. 14 = [𝐻 ] = [𝐻2𝑃𝑂4 ]
2− 3−
● Same procedure for [𝐻𝑃𝑂4 ] and [𝑃𝑂4 ] using
−
the [𝐻2𝑃𝑂4 ]
 ●
+
When 1 drop of 𝐻 is added (1 drop = 0.006 → EXAMPLE
+ −
mol) (using the same conditions above). What is ● 0.5M 𝐻2𝑆𝑂4 ⇔ 𝐻 + 𝐻𝑆𝑂4 , 𝐾𝑎 1 = 𝑙𝑎𝑟𝑔𝑒
− +
the pH of the solution? (𝑂𝐴𝑐 + 𝐻 → 𝐻𝑂𝐴𝑐) − +
𝐻𝑆𝑂4 ⇔ 𝐻 + 𝑆𝑂4 , 𝐾𝑎 2 = 1. 1 × 10
2− −2

I[HOAc] = 0.25M x 0.3L; I[OAc] = 0.56M x +

0.3L Using molar ratios, [ ] of 𝐻 and 𝐻𝑆𝑂4 are 0.5M

A B C

I 0.168 0.0750

Add 0.006 A B C

C -0.006 -0.006 +0.006 I 0.5 0.5

E 0.162 O 0.0310 C -x +x +x
0.3 0.3

[A] = 0.54M; [C] = 0.27M E 0.5 - x 0.5 + x x

−
[𝑂𝐴𝑐 ]
𝑝𝐻 = 𝑝𝐾𝑎 + 𝑙𝑜𝑔( [𝐻𝑂𝐴𝑐] ) = 5. 04
(0.5+𝑥)𝑥 0.5𝑥 2−
− 𝐾𝑎 2 = = = 𝑥 = [𝑆𝑂4 ]
● When 1 drop of 𝑂𝐻 is added (using the same (0.5−𝑥) 0.5

conditions above). What is the pH of the

− − +
solution? (𝐻𝑂𝐴𝑐 + 𝑂𝐻 → 𝐻2𝑂 + 𝑂𝐴𝑐 ) [𝐻 ] = 0. 5𝑀 + 𝑥 = 0. 51𝑀
−
[𝐻𝑆𝑂4 ] = 0. 5𝑀 − 𝑥 = 0. 49𝑀
→ Dilute concentrations
A B C
● EXAMPLE
I 0.075 0.168 ○
−8
[HCl] = 10 M; pH = 8 (not believable)
+ −
Add 0.006 𝐻𝐶𝑙 → 𝐻 + 𝐶𝑙
−
𝐻2𝑂 + 𝐻2𝑂 ⇔ 𝐻3𝑂 + 𝑂𝐻
C -0.006 -0.006 +0.006

E 0.00690 0 0.174
0.3 0.3 A B C
[A] = 0.23; [C] = 0.58
−
[𝑂𝐴𝑐 ]
I 10
−8
𝑝𝐻 = 𝑝𝐾𝑎 + 𝑙𝑜𝑔( [𝐻𝑂𝐴𝑐] ) = 5. 14
→ Buffer ranges C +x +x
● pKa -1 < pH < pKa + 1
E 10
−8
+x x
○ If the buffer is outside of this range, it is
ineffective
−14 −8
● EXAMPLE 𝐾𝑛= 10 = (10 + 𝑥)𝑥
○ If pKa = 4.74, buffer range: 3.74 to 5.74 2
0 = 𝑥 + 10 𝑥 − 10
−8 −14

−8
𝑥 = 9. 51 × 10 𝑀
+ −8 −7
[𝐻 ] = 10 𝑀 + 𝑥 = 10. 5 × 10 𝑀
pH = 6.98
→ Hydrolysis of ions ● 0.1M HOAc + 0.1M HCl, 𝐾𝑎 = 1. 8 × 10
−5

−
● EQUATION 8: 𝐾𝑤 = 𝐾𝑎𝐾𝑏 = [𝐻3𝑂][𝑂𝐻 ] 𝐻𝑂𝐴𝑐 ⇔ 𝐻 + 𝑂𝐴𝑐
+ −

−14
○ 𝐾𝑤 = 10
● Salts: A B C
○ SA + SB - pH = 7
○ WA + WB - pH > 7 I 0.1 0.1
○ SA + WB - pH < 7 C -x +x +x
→ EXAMPLES
−10 E 0.1 - x 0.1 + x x
● 0.5 NaCN, 𝐾𝑎 = 6. 2 × 10 , pH = ?
− −
𝐶𝑁 + 𝐻2𝑂 ⇔ 𝐻𝐶𝑁 + 𝑂𝐻
(0.1 + 𝑥)𝑥 0.1𝑥
𝐾𝑎 = 0.1 − 𝑥
= 0.1
=𝑥
−5 −
1. 8 × 10 = [𝑂𝐴𝑐 ]
A B C + −5
[𝐻 ] = 0. 1 + 1. 8 × 10 = 0. 1𝑀
I 0.5 pH = 1.00

C -x +x +x

E 0.5 - x x x

−
[𝐻𝐶𝑁][𝑂𝐻 ]
𝐾𝑏 = −
[𝐶𝑁 ]
2 2
𝑥 𝑥 𝐾𝑤
= 0.5−𝑥
= 0.5
= 𝐾𝑎
2 −14
𝑥 10
= 0.5
= −10
6.2×10
−3 −
𝑥 = 2. 8 × 10 𝑀 = [𝑂𝐻 ]
pOH = 2.55
pH = 11.45
−5
● 0.1 HOAc, 𝐾𝑎 = 1. 8 × 10
+ −
𝐻𝑂𝐴𝑐 ⇔ 𝐻 + 𝑂𝐴𝑐

A B C

I 0.1

C -x +x +x

E 0.1 - x x x

2 2
𝑥 𝑥
𝐾𝑎 = 0.1−𝑥
= 0.1
−5 −3
𝑥= 0. 1(1. 8 × 10 ) = 1. 34 × 10 𝑀
+
𝑥 = [𝐻 ]
pH = 2.87