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Acids & Bases Edward Wen, PhD
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Types of Ionic Compounds
Acids = form H+ ions in water solution Bases = combine with H+ ions in water solution increases the OH- concentration may either directly release OH- or pull H+ off H2O Salts = Ionic compounds formed from Acid and Base. Example: CaCl2 (from HCl (acid) + Ca(OH)2 (base))
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Properties of Acids Sour taste react with “active” Metals
i.e. Al, Zn, Fe, but NOT w/ Ag, Au Zn + 2 HCl ® ZnCl2 + H2 react with Carbonates, producing CO2 marble, baking soda, limestone CaCO3 + 2 HCl ® CaCl2 + CO2 + H2O change color of vegetable dyes blue litmus turns red react with Bases to form ionic salts
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Properties of Bases also known as alkalis taste bitter
solutions feel slippery change color of vegetable dyes different color than acid red litmus turns blue react with acids to form ionic salts neutralization
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Structure of Bases most ionic bases contain OH- ions
Drano clog-remover: NaOH, Ca(OH)2 some contain CO32- ion: it produces OH- with water Baking soda: CaCO3 Alka-Seltzer: NaHCO3 molecular bases that react with H+ Windex: Ammonia (NH3)
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Acid-Base Theories: An Evolution
Arrhenius’ Theory (1880): H+ vs. OH- Brønsted–Lowry’s Theory (1920’s): H+ donor vs. acceptor Lewis’ Theory: electron pair (lone pair) acceptor vs. donor
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The Arrhenius Definition of Acids
Acids ionize in water to produce H+ ions and anions HCl(aq) → H+(aq) + Cl–(aq) H2SO4(aq) → 2H+(aq) + SO42-(aq)
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The Arrhenius Definition of Bases
Bases dissociate in water to produce OH- ions and cations NaOH(aq) → Na+(aq) + OH–(aq) Molecular compounds containing an OH group, such as methanol, CH3OH, do not dissociate in solution and therefore do not act as bases.
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The Arrhenius Definition of Neutralization
Under the Arrhenius definition, acids and bases naturally combine to form water, neutralizing each other in the process.
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The Brønsted–Lowry Definition of Acids and Bases
Acid—An acid is a proton donor. Example: HF H+ + F- Base—A base is a proton acceptor. Example: OH- + H+ H2O F- + H+ HF
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The Brønsted–Lowry Definition of Acids
HCl is a Brønsted–Lowry acid because, in solution, it donates a proton to water. Ionization of HCl in water to form H3O+ (hydronium ion).
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Ammonia as Brønsted–Lowry Base
NH3 is NOT considered as Arrhenius base since it does not inherently contain OH− ions. However, NH3 is a Brønsted–Lowry base because it accepts a proton from water.
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Brønsted–Lowry definition: Acids (H+ donors) and Bases (H+ acceptors) always occur together
In the following reaction, HCl is the proton donor (acid) and H2O is the proton acceptor (base). In the following reaction, H2O is the proton donor (acid) and NH3 is the proton acceptor (base).
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What happens when an equation representing Brønsted–Lowry acid–base behavior is reversed?
Initially NH4+ : proton donor (acid) OH− : proton acceptor (base). So the change is NH3 (BL base) NH4+ (BL acid) H2O (BL acid) OH− (BL base) NH3 and NH4+ : Conjugate Acid–Base pair
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Conjugate Acid–Base pair
Any two substances related to each other by the transfer of a proton can be considered a conjugate acid–base pair.
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Identifying Brønsted–Lowry Acids and Bases and Their Conjugates
In an acid–base reaction: A base accepts a proton and becomes a conjugate acid. An acid donates a proton and becomes a conjugate base .
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Structure of Acid: Binary acids
(HmX): acid hydrogens attached to a nonmetal atom HCl, HF Hydrofluoric acid
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Oxyacids acid hydrogens (H+) attached to an oxygen atom
H2SO4, HNO3, H3PO4 HClO4
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Organic Acids: Carboxylic acids
-COOH group HC2H3O2, H3C6H5O3 only the first H in the formula is acidic the H is on the COOH
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Most food contains acids
Citric acid (HO2CCH(CO2H)COHCO2H): citrus fruits, tomato Malic acid (HO2CCH2CHOHCO2H): green apple, tomato, grape Ascorbic acid (aka Vitamin C) Folic acid
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Common Acids
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Common Bases
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Acid-Base Reactions (Neutralization, Double Displacement Reaction)
H+ (from the acid) + OH- (from the base) H2O it is often helpful to think of H2O as H-OH Cation (from base) + Anion (from acid) Salt acid + base → salt + water HCl(aq) + NaOH(aq) → NaCl(aq) + H2O(l)
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Acid Reactions. I. Reaction with Metals
Reaction with many metals: Al, Zn, Fe, Mg but not all!! Not for Cu, Au, Ag, etc. Producing a Salt and hydrogen gas H2 3 H2SO4(aq) + 2 Al(s) → Al2(SO4)3(aq) + 3 H2(g)
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Acid Reactions. II Reaction with Metal Oxides
when acids react with metal oxides, they produce a salt and water 3 H2SO4 + Al2O3 → Al2(SO4)3 + 3 H2O
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Acid Reactions. III Gas-evolving Reaction with Salts
when acids react with metal carbonate, bicarbonate, sulfide, sulfite, and bisulfite, gas will be produced along with other products 2 HNO3 + FeCO3 → Fe(NO3)2 + CO2 + H2O HCl + NaHCO3 → NaCl + CO2 + H2O ZnS + 2 HBr → ZnBr2 + H2S CaSO3 + 2 HI → CaI2 + SO2 + H2O H2SO4 + 2 NH4HSO3 → (NH4)2SO4 + 2SO2 + 2H2O
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2 NaOH + 2 Al + 6 H2O → 2 NaAl(OH)4 + 3 H2
Base Reactions Neutralization of acids Reaction with Nonmetal oxides, CO2 2 NaOH + CO2 → Na2CO3 + H2O Strong bases will react with Al metal to form sodium aluminate and hydrogen gas Example: Dissolving recycled aluminum can with NaOH solution 2 NaOH + 2 Al + 6 H2O → 2 NaAl(OH)4 + 3 H2
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Titration Purpose: using Reaction Stoichiometry to determine the Concentration of an unknown solution Titrant (unknown solution) added from a Buret Indicators: chemicals added to help determine when a reaction is complete the Endpoint of the titration occurs when the reaction is complete
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Titration: Color change w/ Indicator
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Titration Start: The base solution as titrant in the buret.
Titrating: As the Base is added to the Acid, H+ + OH– HOH. But still excess Acid present so the color does not change. Endpoint: just enough Base to neutralize all the acid. The indicator changes color.
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Example: Acid-Base Titration
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Example: The titration of mL of HCl solution of unknown concentration requires mL of M Ba(OH)2 solution to reach the endpoint. What is the concentration of the unknown HCl solution?
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Collect Needed Equations and Conversion Factors:
Example: The titration of mL of HCl solution of unknown concentration requires mL of M Ba(OH)2 solution to reach the end point. What is the concentration of the unknown HCl solution? Information Given: mL HCl 12.54 mL M Ba(OH)2 Find: M HCl Collect Needed Equations and Conversion Factors: 2 HCl(aq) + Ba(OH)2(aq) → BaCl2 (aq) + 2H2O(l) 2 mole HCl = 1 mole Ba(OH)2 0.100 M Ba(OH)2 0.100 mol Ba(OH)2 1 L sol’n
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Example: The titration of 10
Example: The titration of mL of HCl solution of unknown concentration requires mL of M Ba(OH)2 solution to reach the end point. What is the concentration of the unknown HCl solution? Information Given: mL HCl 12.54 mL Ba(OH)2 Find: M HCl CF: 2 mol HCl = 1 mol Ba(OH)2 0.100 mol Ba(OH)2 = 1 L M = mol/L Write a Solution Map: mL Ba(OH)2 L Ba(OH)2 mol Ba(OH)2 mol HCl mL HCl L HCl
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2.50 x 10-3 mol HCl 1.25 x 10-3 mol Ba(OH)2 2.50 x 10-1 M HCl
Example: The titration of mL of HCl solution of unknown concentration requires mL of M Ba(OH)2 solution to reach the end point. What is the concentration of the unknown HCl solution? Given: mL HCl 12.54 mL Ba(OH)2 Find: M HCl CF: 2 mol HCl = 1 mol Ba(OH)2 0.100 mol Ba(OH)2 = 1 L 2.50 x 10-3 mol HCl 1.25 x 10-3 mol Ba(OH)2 2.50 x 10-1 M HCl
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Strong Acids Stomach acid HCl ® H+ + Cl- The stronger the acid, the more willing it is to donate H+ use water as the standard base Strong acids donate practically all their H+ 100% ionized in water [H3O+] = [strong acid] [ ] = molarity
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Strong Acids Examples: Binary Acid: HCl, HBr, HI
Oxyacid: HNO3, H2SO4, HClO4, HClO3 Example: HNO3 = H+ + NO3- H2SO4 = 2H+ + SO42-
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Weak Acids Weak acids donate a small fraction of their H+
Vinegar HC2H3O2 Û H+ + C2H3O2- Weak acids donate a small fraction of their H+ most of the weak acid molecules do not donate H+ to water [H3O+] << [weak acid]
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Weak Acids Examples: Binary Acid: HF, H2S, H2Se
Oxyacid: HNO2, H2SO3, H3PO4, HClO Most carboxylic acids, such as acetic acid
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Strong Bases The stronger the base, the more willing it is to accept H+ use water as the standard acid Strong bases: practically all molecules are dissociated into OH– or accept H+ 1 mol NaOH = 1 mol OH- 1 mol Ca(OH)2 = 2 mol OH- [OH–] = [strong base] x (# OH) DranoTM NaOH ® Na+ + OH-
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Weak Bases Definition: a small fraction of molecules accept H+
most of the weak base molecules do not take H+ from water [HO–] << [weak base] WindexTM NH3 + H2O Û NH4+ + OH-
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Weak Acids or Weak Bases remain undissociated in solution
Weak acids (acetic acid, nitrous acid, hydrofluoric acid, etc), Weak base (ammonium hydroxide, etc), Insoluble salts largely remain undissociated in water HC2H3O2(aq) H+(aq) + C2H3O2-(aq) NH4OH(aq) NH4+(aq) + OH-(aq) PbCl2(s) CaCO3(s) BaSO4(s) 42
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Ionic equation involving weak acid/base
Na2CO3(aq) + 2 HC2H3O2(aq) ® 2 NaC2H3O2(aq) + CO2(g) + H2O(l) sol. salt weak acid sol. salt nonelectrolyte 2Na+(aq) + CO32−(aq) + 2HC2H3O2(aq) ® 2Na+(aq) + 2C2H3O2−(aq) + CO2(g) + H2O(l) NIE: CO32−(aq) + 2HC2H3O2(aq) ® 2C2H3O2−(aq) + CO2(g) + H2O(l) Tro: Chemistry: A Molecular Approach, 2/e 43
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Ionic equation involving weak acid/base
NH4OH(aq) + HC2H3O2(aq) ® NH4C2H3O2(aq) + H2O(l) weak base weak acid sol. salt nonelectrolyte NH4OH(aq) + HC2H3O2 (aq) ® C2H3O2−(aq) + NH4+(aq) + H2O(l) NIE: no spectator ions, same as Complete Ionic Equations 44
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Autoionization of Water
Water: extremely Weak electrolyte therefore there must be a few ions present about 2 out of every 1 billion water molecules form Ions: Autoionization H2O + H2O Û H3O+ + OH– H2O Û H+ + OH– ALL aqueous solutions contain both H+ and OH– the concentration of H+ and OH– are equal in water @ 25°C: [H+] = [OH–] = 10-7M
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Ion Product of Water [H+] x [OH–] = constant: Ion Product of water, Kw
At 25°C, [H+] x [OH–] = 1 x = Kw as [H+] increases, [OH–] must decrease so the product stays constant [H+] = 1 x / [OH–] [OH–] = 1 x / [H+]
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Acidic and Basic Solutions
Neutral solutions have equal [H+] and [OH–] [H+] = [OH–] = 1 x 10-7 M Acidic solutions : [H+] > [OH–] [H+] > 1 x 10-7 M [OH–] < 1 x 10-7 M Basic solutions: [OH–] > [H+] [H+] < 1 x 10-7 M [OH–] > 1 x 10-7 M
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Example - Determine the [H+] for a 0
Example - Determine the [H+] for a M Ba(OH)2 and determine whether the solution is acidic, basic or neutral [H+] = 2.5 x M; basic
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All [H+] compared to 1 x 10-7 M [HCl] = 1.0 M
Practice - Determine the [H+] concentration and whether the solution is acidic, basic or neutral for the following All [H+] compared to 1 x 10-7 M [HCl] = 1.0 M [NaOH] = M [H+] = [HCl] = 1.0 M 4.00 x M
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Acidic/Basic: [H+] vs. [OH-]
Base [H+] OH- H+ [OH-] even though it may look like it, neither H+ of OH- will ever be 0 the sizes of the H+ and OH- are not to scale because the divisions are powers of 10 rather than units
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pH The measure of the acidity/basicity of a solution
pH = -log[H+], [H+] = 10-pH exponent on 10 with a positive sign pHwater = -log[10-7] = 7 need to know the [H+] concentration to find pH pH < 7 : Acidic; pH > 7 : Basic pH = 7 : Neutral
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pH scale pH↓, Acidity↑ pH↑, basicity↑ normal range 0 to 14
1 pH unit corresponds to a factor of 10 difference in acidity normal range 0 to 14 pH 0 is [H+] = 1 M, pH 14 is [OH–] = 1 M
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pH measurement pH can be measured by pH meter:
The change in [H+] affects the voltage of a standard cell
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pH of Common Substances
1.0 M HCl 0.0 0.1 M HCl 1.0 stomach acid 1.0 to 3.0 lemons 2.2 to 2.4 soft drinks 2.0 to 4.0 plums 2.8 to 3.0 apples 2.9 to 3.3 cherries 3.2 to 4.0 unpolluted rainwater 5.6 human blood 7.3 to 7.4 egg whites 7.6 to 8.0 milk of magnesia (sat’d Mg(OH)2) 10.5 household ammonia 10.5 to 11.5 1.0 M NaOH 14
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Example - Calculate the pH of a 0
Example - Calculate the pH of a M Ba(OH)2 solution & determine if is acidic, basic or neutral [H+] = 5.0 x M; pH = 11.3
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Example - Calculate the pH of the following strong acid or base solutions
M HCl M Ca(OH)2 [H+] = M, pH = 2.7 [H+] = 1 x M, pH = 12.0
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H+ OH- pH in everyday life
Stomach acid Vinegar Pure water Windex Drano Acid Base pH [H+] OH- H+ [OH-]
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Example - Calculate the concentration of [H+] for a solution with pH 3
[H+] = M
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How does pH change for certain solutions?
Initial pH pH after adding 1 mL 1 M HCl pH after adding 1 mL 1 M NaOH 1 L Pure water 7.00 4.00 10.00 1 L 0.14 M K2HPO M KH2PO4 6.99 7.01
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How does pH change for certain solutions?
Add 1.0 mL 1.0 M HCl solution to 1.0 L of pure water, pH changes from 7.0 to 4.0 (ΔpH = -3.0) Add 1.0 mL 1.0 M HCl solution to 1.0 L of 0.14 M K2HPO M KH2PO4 solution, pH changes from 7.0 to 6.99 (ΔpH = -0.01) Add 1.0 mL 1.0 M NaOH solution to 1.0 L of pure water, pH changes from 7.0 to 10.0 (ΔpH = +3.0) Add 1.0 mL 1.0 M NaOH solution to 1.0 L of 0.14 M K2HPO M KH2PO4 solution, pH changes from 7.0 to 7.01 (ΔpH = +0.01)
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Buffers The mixture of 0.14 M K2HPO M KH2PO4 solution has much smaller pH change when strong acid or base is added, thus is called Buffer. Definition: solutions that resist changing pH when small amounts of acid or base are added Ingredient: mixing together a weak acid and its conjugate base or weak base and it conjugate acid Human body fluid as buffer: H2CO3/HCO3-
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Buffer Composition: a weak acid + its salt;
example: HC2H3O2 / NaC2H3O2 When acid is added: C2H3O2- + H+ HC2H3O2 When base is added: OH- + HC2H3O2 C2H3O2- + H2O OR, a weak base + its salt example: NH3 / NH4Cl
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Acetic Acid/Acetate Buffer
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Treasure Hunt: Which of the following pairs of compounds can combine into a Buffer?
NH3 /NH4Cl HC2H3O2/NaC2H3O2 KNO3/HNO3 Na2SO4/H2SO4 KOH/H2O NH3 /NH4F NH3 /NH4NO3 KNO2/HNO2 Hint: Which is strong acid? Which is strong base? a, b, f, h
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Ba(OH)2 = Ba2+ + 2 OH– therefore
Example - Determine the [H+] for a M Ba(OH)2 and determine whether the solution is acidic, basic or neutral Ba(OH)2 = Ba OH– therefore [OH–] = 2 x = = 4.0 x 10-4 M [H+] = 2.5 x M
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Practice - Determine the [H+] concentration and whether the solution is acidic, basic or neutral for the following All [H+] compared to 1 x 10-7 M [OH–] = 3.50 x 10-8 M [NaOH] = M [Ca(OH)2] = 0.20 M [HCl] = 1.0 M
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More Practice - Determine the [H+] concentration and whether the solution is acidic, basic or neutral for the following [OH–] = 3.50 x 10-8 M NaOH = M Ca(OH)2 = 0.20 M [H+] = 1 x 10-14 3.50 x 10-8 = 2.86 x 10-7 M [H+] >[OH-], therefore acidic [H+] = 1 x 10-14 = 4.00 x M [H+] < [OH-], therefore basic [OH-] = 2 x 0.20 = 0.40 M [H+] = 1 x 10-14 4.0 x 10-1 = 2.5 x 10-14 [H+] < [OH-], therefore basic
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Example - Calculate the pH of a 0
Example - Calculate the pH of a M Ba(OH)2 solution & determine if is acidic, basic or neutral Ba(OH)2 = Ba OH- therefore [OH-] = 2 x = = 2.0 x 10-3 M [H+] = 1 x 10-14 2.0 x 10-3 = 5.0 x M pH = -log [H+] = -log (5.0 x 10-12) pH = 11.3 pH > 7 therefore basic
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Example - Calculate the pH of the following strong acid or base solutions
M HCl HCl as strong acid, so [H+] = M pH = - log (2.0 x 10-3) = 2.7 M Ca(OH)2 Ca(OH)2 as strong base, so [OH-] = M [H+] = 1 x 10-14 1 x 10-2 = 1 x M pH = - log (1.0 x 10-12) = 12
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Example - Calculate the concentration of [H+] for a solution with pH 3
= 2 x 10-4 M = M
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