Chem 17 Review

Chemical Equilibrium

Reversible reactions

- Do not go to completion
- They can occur in either direction

Chemical equilibrium exists when two opposing reaction occur simultaneously at the same rate

- Reversible system @ Chemical equilibrium when:

o Forward reaction rate = Reverse reaction rate
o No change in amounts

Chemical equilibria is a dynamic process

- Molecules are continually reacting

o The overall composition of the reaction mixture does not change

Equilibrium can be established from either the forward or reverse direction

One-step mechanism reversible reaction:

- Rateforward = kforward[A][B] (Reactants: A and B)

- Ratereverse = kreverse[C][D] (Products: C and D)

System @ Equilibrium

- Ratef = Rater
o Derivation
o Kc – new constant (from kf/kr)
o Kc = [C][D]/[A][B] (Product over reactant)

For general reactions

- Keq = Activity of productscoefficients/activity of reactantscoefficients

- Activity of species
𝛾𝑖 [𝑖(𝑠𝑝𝑒𝑐𝑖𝑒𝑠)]
o 𝑎𝑖 = 𝑐°
▪ 𝑎𝑖 - activity of species (i)
𝛾𝑖 – activity coefficient of species (i)
𝑐 ° - referencing unit
▪ At low concentrations (dilute, ideal solutions)
• Activity coefficient of species is 1
o As such: activity is now equal to concentration of species
o At ideal conditions
[𝐶]𝑐 [𝐷]𝑑 1 ∆𝑛
▪ Kc is equal to [𝐴]𝑎[𝐵]𝑏 (𝑐 °)
 1 ∆𝑛
( °) – referencing unit
𝑐
▪ Kc – Dimensionless

Relationship of K to the balanced chemical equation

- When equation is reverse

o The value of K is inverted
- When the coefficients were multiplied by a common factor
o The equilibrium constant is raised to the corresponding power
- When divided by a common factor
o Corresponding root of the equilibrium constant

Combining Equilibrium Constant Expressions

- When individual equations are combined

o Their equilibrium constants are multiplied = equilibrium constant for the overall
reaction

Variation of Kc with the form of the balanced equation

- Large Kc
o Most of the reactants are converted to products
- Small Kc
o Small amounts of products are formed

- 2 main calculations:
o Using ICE table
▪ Equilibrium concentrations -> Kc
▪ Kc -> Equilibrium concentrations

Predicting the direction of reactions: The REACTION COEFFICIENT, QC

- Mass action expression/reaction quotiemt

o Q
o Has the same form as KC
- Concentrations used in Q are Not equilibrium values
The Reaction Quotient

- To predict how the equilibrium will respond to an applied stress

o Compare Q with KC
▪ Q = KC : in Equilibrium (Stable condition)
▪ Q > KC : Towards Reactants (<-)
▪ Q < KC : Towards Products (->)

Disturbing a system at Equilibrium: Le Chatelier’s Principle

- Le Chatelier’s Principle – if a change of conditions (stress) is applied to a system in equilibrium

o The system responds in the way that best tends to reduce the stress in reaching a new
state of equilibrium
o Stresses
▪ Change in Concentrations
▪ In pressure/volume (for gaseous reactions)
• Less volume, more pressure
o Toward products
• More volume, less pressure
o Toward reactants
▪ In Temperature
• Depend on the sign of deltaH reaction
o Introduction of a catalyst
▪ Catalysts decrease the activation energy of both the forward and reverse
reaction equally
o Catalysts the position of the reaction relative to the equilibrium state
▪ The concentrations of the products and reactants will be the same
• Whether a catalyst is introduced or not at equilibrium
• With a catalyst
o Equilibrium will be established faster

Equilibrium Constant Expression in Gas-Phase Reactions

- Equilibrium constants can be expressed in

o Partial pressures
Rather than concentrations
o KP
- For gases
o Pressure is proportional to concentration
▪ P = MRT
M = P/RT
- For Calculations:
o KC = KP x (RT)-1
 R = 0.0821 (L)(atm)(mol)-1(K)-1

Relationship Between Kp and Kc

- Kc = Kp(RT)-dn
dn = # of moles of gaseous products - # of moles of gaseous reactants

Heterogeneous Equilibria

- Have more than one phase present

- Difference of equilibrium constant
o Pure solids and liquids have activities of unity
o Solvents in very dilute solutions have activities that are essentially unity

Gibbs’ Free Energy and equilibrium

- With circle – standard

o Otherwise – nonstandard conditions
- ∆𝐺 = ∆𝐺 ° + 𝑅𝑇 𝑙𝑛𝑄
- ∆𝐺 = ∆𝐺 ° + 2.303 𝑅𝑇 𝑙𝑜𝑔𝑄
- @ Equilibrium
o ∆𝐺 = 0 and
o Q=Kc
o ∆𝐺 ° = −2.303 𝑅𝑇 𝑙𝑜𝑔𝐾
∆𝐺 ° = −𝑅𝑇 𝑙𝑛𝐾
▪ THERMODYNAMIC FORM
Used when both gaseous and solution forms appear in the chem equation
▪ Conditions
• ∆𝐺 ° rxn < 0 | K > 1
o Forward rxn spon.
More products @ equilibrium
• ∆𝐺 rxn = 0 | K = 1
°

o Ideal system, very rare

• ∆𝐺 rxn > 0 | K < 1
°

o Reverse rxn spon.

More reactants @ equilibrium

Evaluation of Equilibrium Constants at different temperatures

- From the value of ∆𝐻 ° and K at one temp (T1)

o Van’t hoff equation to estimate the value of K at another temp (T2)
 𝐾𝑇2 ∆𝐻 ° 1 1
o 𝑙𝑛 𝐾 = (
𝑅 𝑇1
−𝑇)
𝑇1 2

Acid and Base Equilibria

Arrhenius definition

- Acid
o Donates hydrogen ion
- Base
o Donates hydroxide ion

Bronsted-Lowry Definition

- Acid
o Donates H+
o Proton donor
- Base
o Accepts H+
o Proton acceptor
- Correct assignment of acid-base conjugate pairs
o Based on properly drawn lewis structures

Amphoterism

- Species that can behave as an acid or base

o Amphoteric
- Amphiprotic
o Special term for an amphoteric species which involves proton transfer reactions to
show behavior as either an acid or base

Lewis definition

- Acids
o Electron pair acceptor
o With H+
o Electron deficient molecules
 - Bases
o Electron pair donor
o With OH-
o With lone e- pairs

Autoionization of water

- Concentration of water is constant (and large) @ 25C

o Experimental concentration H+ is 1.00x10-7
▪ Kw = 1.00 x 10-14
• pH + pOH = 14

Relative strengths of acids and bases | Conjugate Acid-Base Pairs

- Weaker acid or base

o Stronger the conjugate partner
- Stronger acid or base
o Weaker the conjugate partner
- Predicting direction of Acid-Base reactions
o Stronger acid and base -> Weaker acid and base

Ionization Constant for Monoprotic Weak Acids and Bases

- Ka – acid-dissociation constant
o Ka = [H+][conjugate base]/[acid]
- Kb – Base dissociation constant
o Kb = [OH-][conjugate acid]/[base]
- HF > HNO2 > CH3COOH > HClO >HCN
- Calculations
o If Ka/CHA < 1.0 x 10-3, use simplifying assumption
o X = squ.rt. of CHA x KA
pH = -log(sq.rt. of ChaKa)
▪ pH = ½(pKa + pCHA)
• Initial pH of a dilute solution of weak acid HA

Percent Ionization of weak Acids/Bases

- %ionized Ha = ([H+(aq)]eq or [A-(aq)]eq/CHA) x100

Solvolysis: Reaction of Acid/Base with solvent

- Solvolysis – reaction of a subsatance with the solvent in which it is dissolved

o Hydrolysis – rxn with water or its ions
o Kb = Kw/Ka
Ka = Kw/Kb
o The stronger the acid/base, the weaker is its conjugate

Strength of Acids and Bases

- Strengths of Binary Acids

o Acid strength increases
▪ With decreasing H-X bond strength
• VIIA hydrohalic acids
o Bond strength
HF >> HCl > HBr > HI
o Acid strength
HF << HCl < HBr < HI
• VIA hydrides
o Bond strength
H2O >> H2S > H2Se > H2Te
o Acid strength
H2O << H2S < H2Se < H2Te
o Down a group
▪ Up size
▪ Down energy to break H- bond
▪ Down electronegativity
▪ Up acidity
o Across a period
▪ Up electronegativity
▪ Up acidity
- Ternary acids
o Hydroxides of nonmetals that produce H3O+ in water
o Consists: H, O, and a nonmetal
o Acidity of ternary acids with same central element increase with increasing oxidation
state of central element, and increasing O atoms
▪ HOWEVER, for phosphorus ternary acids
• H3PO2 > H3PO3 > H3PO4
• Relative position of H is important
- Base Strength of Amines
o Amines
▪ Organic molecules with basic N as functional group
▪ Can be: (depending on the number of R groups attached on the N)
• Primary
 • Secondary
• Tertiary
▪ Basicity are described by
• The electronic properties of the substituent groups attached to N
o Alkyl groups
▪ Donate e density
o Halides and aromatic groups
▪ Withdraw e density
• Steric hindrance offered by the groups on nitrogen
• Dimethylamine is more basic than methylamine
o because it has 2 -CH3 groups that enhance e- of lone pair
• Trimethylamine has lower basicity
o since the 3 -CH3 groups hinder the e pair
▪ difficult to accept H+
• Propylamine and 2-propylamine are more basic
o Because of larger R groups
▪ More e- property

Polyprotic Acids/Bases

- Many weak acids contain two or more acidic hydrogens

- Calculation of equilibria for polyprotic acids is done in a stepwise fashion
o There is a dissociation constant for each step
o Ka1 is almost always higher than the succeeding dissociation constants
o Negative charge further prevents H+ from leaving the species
▪ Thereby diminishing the Ka value

Solvolysis/Hydrolysis of polyprotic acids

- Hydrolysis of Diprotic Acid, H2A

o The pairing of Ka and Kb values for diprotic acids are based on Kw
▪ But through the extremes of each conjugate form
o Kb1 should be > Kb2
▪ Since it is the first base dissociation process
o Stronger the acid/base
▪ Weaker is it conjugate
o Ka1 x Kb2 = Kw
Ka2 x Kb1 = Kw
- For triprotic acid
o Ka1 x Kb3 = Kw
Ka2 x Kb2 = Kw
Ka3 x Kb1 = Kw

Acidity or basicity of amphiprotic species

- The behavior of an amphiprotic species

o Depend on the magnitude of dissociation constants
Inorganic Lewis Acids – Hydrolysis of Metal Ions

- Metal ions (positively charged)

o Attract electrons of oxygen atoms in water
▪ Depending on the strength of electron interacting with the cation
• The water molecule can turn into hydroxide anion and release H+
o The acid strength of these ion-complexes acting as lewis acids
▪ Depend on size and charge of cation center

Salts of acids and bases

- Aq. Solutions of salts of strong acids and strong bases

o Neutral
- Aq. Solutions of salts of strong bases and weak acids
o Basic
- Aq. Solutions of salts of weak bases and strong acids
o Acidic
- Aq. Solutions of salts of weak bases and weak acids
o Neutral
o Basic
o Acidic
o pH determined by
▪ Ka
▪ Kb

Common Ion effect

- Le Chatelier-based shift
- Direction of shift of eq. is always towards the side that diminishes the added common/similar ion

Buffers

- Solutions that contain both acid component and its conjugate base
o Conjugate base is present in the initial concentration of components
- Resist drastic pH changes

Henderson-Hasselbalch Equation

- pH = pKa + log [salt]/[acid]

- pOH = pKb + log [salt]/[base]
- only used when salt is present
o present separately
o not the [salt] from ICE calculation
- the salt component must be added separately
o or, generated by neutralizing the main component
- calculations
o ICE table
 ▪ Must be in moles esp. if volumes are not same
o Ka
▪ Molarity
- Allowed only when “simplifying assumptions” are valid

Preparation of Buffers

- In 3 ways
o Adding a solid salt component to a liquid
o Neutralizing a liquid component with a strong opposite component
o Mixing 2 solid salts in the same volume water

Buffers and Common ion effect

- Common ion effect applies to buffer systems as well

- | dpH |=|pHi – pHf|

Buffer Capacity

- Measure of buffering effectivity

∆𝑩
- 𝜷 = ∆𝒑𝑯
o ∆𝑩
▪ # of moles of acid/base added per 1L of buffer solution
o ∆𝒑𝑯
▪ Change in pH associated with the addition of acid/base
- Amount of acid or base (mL) needed to change the pH of a buffer solution by 1 degree
- Buffer capacity is highest when pH = pKa

Acid- Base Indicators

- Equivalence point
o The point at which chemically equivalent amounts of acid and base have reacted
- End point
o The point at which a chemical indicator changes color
[𝑯𝟑𝑶+][𝑰𝒏−]
o 𝑲𝒊𝒏 = [𝑯𝑰𝒏]
o [H3O+]
▪ pH range when indicator changes its color
• depends largely on Ka of the indicator
o Methyl Violet
▪ Acid
• yellow
▪ pH range
• 0-2
▪ Basic
• Purple
 o Methyl Orange
▪ Acid
• pink
▪ pH range
• 3.1 – 4.4
▪ Basic
• yellow
o Litmus
▪ Acid
• Red
▪ pH range
• 4.7 – 8.2
▪ Basic
• blue
o Phenolphthalein
▪ Acid
• colorless
▪ pH range
• 8.3 – 10.0
▪ Basic
• Red

Titration Curves

- Y-axis
o pH of solution
- X-axis
o Volume of added titrant
- Strong acid/strong base titration curve
o Methyl violet cannot be used as indicator in the titration because the change in color is
away from inflection curve/equivalence point
- Weak acid with strong base
o Methyl orange and methyl violet cannot be used
o Initial region
▪ Use ICE and Ka: pH = ½ (pKa + pCHA)
o Half equivalence point
▪ pH = pKa
▪ Buffer region: HH Equation
• pH = pKa + log (moles A-/moles HA)
• pH = pKa + log [moles titrant/(moles analyte – moles titrant)]
o Excess base regiom
▪ pOH = -log (moles excess base/total volume)
o Equivalence region
▪ Use ICE and Kb: pOH = ½ (pKb + p[moles HA/total volume])
Solubility equilibria

Saturated solution

- Equilibrium is established between dissolved and undissolved solutes

o Ex. Air – 100% humidity
- Eventually the rate of dissolution will equal the rate of precipitation
o The ions will continue to dissolve and precipitate
o Solute at first only dissolves

Supersaturated solutions

- Higher-than-saturated concentrations of dissolved solutes

NaCl

- Very high solubility in water

- Reaction is shifted forward or toward formation of hydrated ions
o Which overall has more negative free energy

Solubility product constant – Ksp

- Silver chloride, AgCl, is rather insoluble in water

o Small amount of AgCl is dissolved
- The concentration of ions are in equilibrium
- Inverse of Ksp is the eq. constant for precipitation
- Same rules apply for compounds that have more than two kinds of ions
- s – molar solubility
- Ksp = nsn
- when comparing the solubility of different salts
o best to look at molar solubility derived from the Ksp
▪ instead of just ksp value

Reaction Quotient Qsp in precipitation reactions

- Qsp, Ksp
o Used to analyze whether or not a precipitate will form upon mixing of two ionic species
o Qsp > Ksp
▪ Precipitation
o Qsp < Ksp
▪ Dissolution

Fractional precipitation

- Precipitating some ions from solution while leaving others in solution

 o Low molar solubility
▪ Precipitate first
o High molar s
▪ Precipitate last
- Calculating minimum amount of Cl- needed to precip. Each species
o [Cl-] = Ksp/[cation]
- %Au+unprecip = [Au]unprecip/[Au]orug x 100%

Simultaneous Equilibria involving slightly soluble compounds

- Eq. that simultaneously involve 2 or more different eq. constant expressions