I.

Definitions

Acids & Bases

Arrhenius Acids
- Strong acids completely ionize in water to release H+ (H3O+) and an anion; know the names & formulas of the strong & weak acids & bases. Strong Acids: HClO4 H2SO4 H3O+ + IHI or HBr HI HCl HNO3 (100%)

A. Arrhenius Acids and Bases H+ + H2O H3O+ Hydronium Ion + in place of H O+; 2) [ ] = m/L = M Note: 1) I will use H 3 Acid: A substance which increases [H+] when dissolved in water. Base: A substance which increases [OH-] when dissolved in water. -The above concepts were introduced by Svante Arrhenius in his doctoral thesis in 1884 in Sweden. His thesis was assumed to be wrong, and he was given the lowest possible passing grade; awarded the Nobel Prize in 1903 for his work!

HI + H2O Notes:

H+ + I-

1) Caution: Strong acids react with proteins, carbohydrates and fats. 2) Caution: HClO4 and HNO3 can react explosively with organics. 3) Only the first ionization is 100% with H2SO4 4) Important: Know the Strong & Weak acids/Bases and their Names. 5) For oxy acids like HNO3 , H2SO4 & HClO4 the acidic H is on an O atom.

Arrhenius Acids
- Weak acids only partially ionize in water; < 5% ionization. Weak Acids: HC2H3O2 HF H3PO4 HCN HC2H3O2 H+ + C2H3O2H2S HNO2 NH4+

Arrhenius Bases
Strong bases ionize 100 % in water and weak bases only partially ionize. Examples of Strong Bases: LiOH NaOH KOH Ca(OH)2 Sr(OH)2 Ba(OH)2 Na3PO4 NH3 CO3-2 HCO3CNC2H3O2F-

(~ 1% ionized)

Examples of Weak Bases: NaOH NH3 + H2O F- + H2O Na+ OH-

Note: - only the H attached to the O in acetic acid is released; Hs attached to C are NOT acidic; most organic acids are weak acids.

+ NH4+ + OHHF + OH-

(strong, 100 % Ionized) (weak, 1 % Ionized) (weak, 1 % Ionized)

H O H C C O H H
- pH, conductivity & vant Hoff factor (i) measurements allow one to experimentally determine the % ionization. - Know the names & formulas of the above weak acids.

Notes: 1) Salts of weak acids are generally weak bases like C2H3O2- & F- are usually found as group I salts like NaF, KF, LiF, NaC2H3O2, etc. 2) Bases are much more damaging to proteins and triglyceride fats than acids. Eye damage can occur on contact; even with dilute bases. 3) Important; know the strong & weak bases/acids & their names.

Arrhenius Acids & Bases

- H+ and OH- are in dynamic equilibria in water; changing the M of one will change the M of the other. - The following equilibria always takes place in water regardless of any other chemical present. H2O H+ + OH-

B. Brnsted-Lowry Acids and Bases

- The Arrhenius definition does not apply when water is not the solvent; so, a broader definition (Brnsted-Lowry) was generated. Acid: Base: A proton donor A proton acceptor
Note: Proton = H+

- [H+] & [OH-] = 1.00x10-7 M for pure water - Notes: 1) Le Chateliers Principle predicts effect of adding additional H+ or OH- to H2O. 2) Acid + Base react completely to yield a salt plus water.
Example: 2HCl + Ca(OH)2 ----) CaCl2 + 2H2O ; NIE: H+ + OH- ----) H2O

Example: HCl (g) + NH3 (g) -----) NH4Cl (s) H+(aq) + :NH3(aq) -----) NH4+(aq)
(Net Ionic Eqn in H2O)

Notes: 1) HCl is the proton donor & NH3 is the proton acceptor 2) The products are called conjugates. 3) The Brnsted-Lowry definition includes all Arrhenius acids and bases plus additional ones.

B. Brnsted-Lowry Acids and Bases

Old Bronsted

B. Brnsted-Lowry & Lewis Acids and Bases

Examples:

HF + HCO3HF = Acid HCO3- = Base

H2CO3 + FF- = Conjugate Base H2CO3 = Conjugate Acid

CH3NH2 + HI ------) CH3NH3+ + IYoung Bronsted

Which is conjugate acid & which is conjugate base? I- = conjugate base CH3NH3+ = conjugate acid

C. Lewis Acids and Bases

- The most general acid-base definition is based on electrons and is called the Lewis definition (same Lewis that gave us Lewis structures).

Lowry

Acid = Electron pair acceptor Base = Electron pair donor

C. Lewis Acids and Bases

Example: AlCl3 + Cl- -----) AlCl4AlCl3 accepts a pair of electrons = Acid Cl- donates a pair of electrons = Base 1) The above is an acid base reaction in the Lewis sense; AlCl3 & Cl- are Lewis acids & bases but not Brnsted or Arrhenius acids & bases. 2) Many organic reactions use non-polar solvents, and non-polar Lewis acids such as AlCl3 BF3 FeCl3 are more soluble than polar acids in the non-polar organic solvents. 3) Lewis definition includes all Arrhenius & Bronsted acids & bases.

II. Acid - Base Strengths

- For two acids that are 100% ionized in water (like HI and HBr),

one uses a solvent other than water (like acetic acid) to compare their strengths. Acetic acid as a solvent cuts down on acid ionization (Le Chatliers Principle). - Table 15.2 is a partial list of the strengths. Organics are left off. Organic acids such as: HC2H3O2 (acetic), HCO2H (formic), HC4H7O2 (butyric), and HOC6H5 (phenol) are weak acids. Organic bases like NH2-CH2-CH2-NH2 are weak bases. O CH3COH O HCOH O CH3CH2CH2COH

-OH

- Organic acids are generally weaker than inorganic acids. Some organic bases like :CH3- are much stronger than inorganic bases.

III. Calculating & Measuring [H+], [OH-]

II. Acid - Base Strengths

- Two factors influence acid strength: 1) Bond Polarity - The more polar the bond, the stronger the acid. - HCl (EN = 0.9) > > H2S (EN = 0.4) - The weaker the bond, the stronger the acid. - HI >> HF. HI bond weaker than HF bond. - Bond strength is the larger of the two factors.

A. Autoionization of Water - The following is always true in water:

H2O Keq =
Note:

H+ + OH[H2O]

M H2O = 55.5 m/L constant or Kw= 1.00x10-14 = [H+][OH-]

[H+][OH-] /

1) Kw incorporates the 55.5 M; Kw = Keq [55.5] = 1.00x10-14 2) H2O drops out of the equil. expression when water is the solvent.

2) Bond Strength

H2O
1.00x10-14 = [H+][OH-] - Let X = M of H2O that dissociates, then 1.00x10-14 = [X] [X] = [X]2 x = [H+] = [OH-] = 1.00x10-7 M

H+ + OHALWAYS TRUE IN WATER X = [H+] = [OH-] at equilibrium

a) Which is the strongest acid: HClO4 or HClO3? b) Which is the strongest acid: FCH2-CO2H or CH3-CO2H? Answers: a) HClO4 b) FCH2-CO2H
(both polarity & bond strength factor in)

X = 1.00x10-14 = 1.00x10-7 (for pure water = neutral solution)

- If add another source of acid or base to water, then 1.00x10-14 = [H+][OH-] is still true; however, [H+] & [OH-] will no longer be equal.

B. Addition of Strong Acid or Base to Water

1) If one adds 0.10 mole of HI to 1.0 L of water, then what is the - Strong acids ionize 100% The M of H+ = M of the strong acid for HI. - 0.10 M HI yields 0.10 M H+ in water 2) What will be the [OH-] in 0.10 M HI? - Need to use: 1.00x10-14 = [H+] [OH-] Note: [H+] = 0.10 M
from: H2O H+ + OH-

B. Addition of Strong Acid or Base to Water continued

- General Rule: The M of H+ or OH- is the M of the strong acid or strong base. - Exception: Above not true when M of the strong acid (or base) is < 10-6 M. - Are two sources of H+ for aqueous acid: One from H2O (~10-7) & one from acid: [H+]total = [H+]H2O + [H+]Acid [H+]total = (~10-7) + [H+]Acid Example: What will be the [H+] if one adds 1.0x10-9 moles of HI to 1.0 L of water? Will the [H+] be 1.0x10-9 M? No: [H+] = (1.0x10-7+ 1.0x10-9) = 1.0x10-7

[H+]?

1.00x10-14 = [0.10] [OH-]

[OH-] = 1.0x10-13 M

C. pH
-

Note: p = mathematical operator = take -log

3) What are the [H+] & [OH-] in 1.0 x 10-2 M NaOH ? - NaOH ionizes 100%. 1.0 x 10-2 M NaOH yields 1.0x10-2 M OH1.00x10-14 = [H+] [OH-] 1.0x10-14 = [H+] [1.0x10-2] [H+] = 1.0x10-12 M

Need a more convenient scale than [H+] for measuring acidity; the [H+] scale is too large from about 10o to 10-14 in water; can compact using the pH scale.

pH = - log [H+]
- Be careful using calculator: 1) What is pH of:

- log [10-x] = x
ln is to the base e & log is to the base 10. 1.0 x 10-5 M HCl? 5.00 5.0 x 10-5 M HCl? 4.30

Note: The following summarizes the acidity scale: [H+] > 1.0x10-7 M = Acidic [H+] = 1.0x10-7 M = Neutral

[H+] < 1.0x10-7 M = Basic

1.0 x 10-4 M HCl? 4.00

C. pH continued
2) if take -log of both sides of: = 14.00 = pH + pOH What is pH if pOH = 11.0? 1.00x10-14 [H+][OH-] , then get:

C. pH
M to pH Example: Convert 4.5x10-3 M H+ to pH

pH = 14.00 pOH = 3.0

3) May have to calculate [H+] from a pH. You need to use 10x, or inverse log, or antilog functions Depending on your calculator. pH = -log [H+] Examples: -What is [H+] if the pH is 5.50? [H+] = 10-5.50 = 3.2 x 10-6 -What is [H+] if the pH is 9.38? [H+] = 10-9.38 = 4.2 x 10-10 4) Can check acidity with either a pH meter or with an Indicator [H+] = 10 - pH

-log 4.5x10-3 = -log 4.5 + -log 10-3 = -0.653 + 3.000 = 2.347 = 2.35 M pH 4.6x10-3 2.3372 4.5x10-3 2.3468 4.4x10-3 2.3565
pH to M Example: Convert pH of 2.34 to M H+

- antilog 2.34 = -antilog 3.00 + antilog 0.66 = 10-3 x 4.57 = 4.6x10-3 - inverse log 2.34 = 10-2.34 = 4.6x10-3 pH M 2.33 4.68x10-3 2.34 2.35 4.57x10-3 4.47x10-3

2 SF

pH Electrodes
M Scale:
- pH meter is a device used to measure potential developed by a set of electrodes (reference and glass). Et = Eglass+ Eref Et converted to pH - The surface of the electrode has special glass which attracts H+ & sets up a potential difference across glass membrane. -Needs to be calibrated with standard buffers. Up to 0.01 accuracy. - Typical combination electrode ($100 to $1000):

Acidity Scale
Acidic Neutral Basic 10-1 10-7 ..... 10-14 pH Scale: 1 .. 7 .. 14 pH < 7 (acidic) pH = 7 (neutral) pH > 7 (basic)

Indicators
Indicators organic compounds whose color varies with acidity. Can coat paper with several indicators and specific color will tell pH to within 1 pH. Predict result of mixing MO & BCG.