Chapter 16. Properties of Bases 5/21/2013. also known as alkalis taste bitter solutions feel slippery. change color of vegetable dyes

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1 Chemistry, The Central Science, 10th edition Theodore L. Brown; H. Eugene LeMay, Jr.; Bruce E. Bursten Chapter 16 John D. Bookstaver St. Charles Community College St. Peters, MO 2006, Prentice Hall, Inc. Properties of sour taste react with active metals recall the activity series (any metals above H are active ) 2 Al (s) + 6 HCl (aq) 2 AlCl 3 (aq) + 3 H 2 (g) corrosive has the ability to eat away/destroy other substances react with carbonates (containing CO 2-3 ) produce CO 2 gas marble, baking soda, chalk, limestone CaCO 3 (A) + 2 HCl (aq) CaCl 2 (aq) + CO 2 (g) + H 2 O (l) change color of vegetable dyes blue litmus paper turns red react with bases to form ionic salts (ionic compounds) Properties of also known as alkalis taste bitter solutions feel slippery Many soaps are manufactured with the use of bases change color of vegetable dyes different color than acid red litmus paper turns blue react with acids to form ionic salts (ionic compounds) This is known as neutralization 1

2 What are? There are several different ways to define the terms acid base Each definition comes from a different acid/base theory: Arrhenius Theory Brønsted-Lowry Theory Lewis Theory Arrhenius Theory Acid: when dissolved in water, the hydrogen ion concentration increases (basically, an Arrhenius acid produces H + ions) Ex) HCl (aq) H + (aq) + Cl (aq) HCl is an acid b/c it is ionized (molecular acid that is pulled apart by water) to form H + Base: when dissolved in water, the hydroxide ion concentration increases (basically, an Arrhenius base produces OH ions) Ex) NaOH (aq) Na + (aq) + OH (aq) NaOH is a base b/c it dissociates (ionic compound breaking up into its ions) to form OH Problems with Arrhenius Theory Does not explain why molecular substances, like NH 3, some ionic compounds, like Na 2 CO 3 or Na 2 O, are bases since they do not contain OH ions, they can t be considered Arrhenius bases Does not explain why molecular substances, like CO 2, dissolve in water to form acidic solutions since it doesn t even contain H + ions it can t be considered an Arrhenius acid Does not explain acid-base reactions that take place outside of aqueous solutions 2

3 Hydronium Ion: H 3 O + the H + ions produced by the acid are so reactive they cannot exist in water H + ions are just protons w/ no valence electrons!!! To be more stable, H + ions react with water molecule(s) to produce hydronium ions, H 3 O + Note: for our purposes, H + H 3 O + will be used interchangeably Brønsted-Lowry Theory The Brønsted-Lowry theory looks at the entire acid-base chemical reaction In an acid-base reaction, an H + is transferred from the acid to the base Broader, more general, definition than Arrhenius does not have to take place in aqueous solution Brønsted-Lowry & Brønsted-Lowry acids are H + donors (aka: proton donors) Must have a removable (acidic) hydrogen because of the molecular structure, often one H in the molecule is easier to transfer than others (this is known as the ionizable hydrogen ) Brønsted-Lowry bases are H + acceptors (aka: proton acceptors) Must have a lone pair/ nonbonding pair of electrons because of the molecular structure, often one atom in the molecule is more willing to accept 9 H + transfer than others 3

4 Brønsted-Lowry Acid/Base Rxns Ex) HCl (aq) + H 2 O (l) Cl (aq) + H 3 O + (aq) acid base HCl transfers an H + to H 2 O, forming H 3 O + ions water acts as base, accepting H + Ex) NH 3 (aq) + H 2 O (l) NH 4 + (aq) + OH (aq) base acid NH 3 (aq) is a Brønsted-Lowry base because NH 3 accepts an H + from H 2 O (it is also an Arrhenius base because it forms OH ) water acts as acid, donating H + Amphiprotic Molecules Amphiprotic (or amphoteric) means have qualities of both substance can act as both an acid a base depending what it is reacting with After Donated H+ Amphoteric Molecule After Accepted H+ OH H 2 O H 3 O + CO 3 2 HCO 3 H 2 CO 3 SO 4 2 HSO 4 H 2 SO 4 Brønsted-Lowry Reversible Acid-Base Reactions Brønsted-Lowry theory allows A-B rxns to be reversible (shown w/ double-sided arrows) General A-B rxn: H A + :B :A + H B + the original base has an extra H + after the reaction, so it will act as an acid in the reverse process the original acid has a lone pair of electrons after the reaction, so it will act as a base in the reverse process :A + H B + H A + :B 4

5 Conjugate Pairs In a Brønsted-Lowry Acid-Base reaction, the original base becomes an acid in the reverse reaction, the original acid becomes a base in the reverse process each reactant the product it becomes are called a conjugate pair the original base becomes the conjugate acid; the original acid becomes the conjugate base Conjugate Pairs Brønsted-Lowry Acid-Base Reactions H A + :B :A + H B + acid base conjugate conjugate base acid HCHO 2 + H 2 O CHO 2 + H 3 O + acid base conjugate conjugate base acid H 2 O + NH 3 OH + NH + 4 acid base conjugate conjugate base acid 5

6 Conjugate Pairs Practice Determine the acid, base, conjugate acid, conjugate base in the following reaction: H 2 O + H 2 SO 4 HSO 4 + H 3 O + base acid conjugate conjugate base acid Arrow Conventions chemists commonly use two kinds of arrows in reactions to indicate the degree of completion of the reactions a single arrow indicates all the reactant molecules are converted to product molecules at the end a double arrow indicates the reaction is in equillibrium. The reaction stops when some of the reactant molecules have been converted into products. Some reactant molecules remain some products molecules have formed Looks like in these notes Strong or Weak a strong acid is a strong electrolyte practically all the acid molecules ionize ( ) a strong base is a strong electrolyte practically all the base molecules form OH ions, either through dissociation or reaction with water ( ) a weak acid is a weak electrolyte only a small % of the molecules ionize ( ) a weak base is a weak electrolyte only a small % of the base molecules form OH ions ( ) 6

7 Autoionization of Water As we have seen, water is amphoteric. In pure water, a few molecules act as bases a few act as acids. about 1 out of every 10 million water molecules form ions through a process called autoionization H 2 O(l) + H 2 O(l) H 3 O + (aq) + OH (aq) all aqueous solutions contain both H 3 O + OH the concentration of H 3 O + OH are equal in pure water (which is neutral) Ion Product of Water the product of the H 3 O + OH concentrations is a constant number the number is called the ion product constant of water (K w ) At 25ºC, [H 3 O + ] [OH ] = [H + ] [OH ] = K w = 1 x if you measure one of the concentrations (H + or OH ), you can calculate the other as [H 3 O + ] increases the [OH ] must decrease so the product stays constant inversely proportional Acidic Basic Solutions all aqueous solutions contain both H + OH ions neutral solutions [H + ] = [OH ] = 1 x 10-7 acidic solutions [H + ] is greater than [OH ] [H + ] > 1 x 10-7 ; [OH ] < 1 x 10-7 basic solutions [OH ] is greater than [ 3 O + ] [OH ] > 1 x 10-7 ; [H + ] < 1 x 10-7 Be careful! We are dealing with NEGATIVE exponents. the larger the negative exponent, the SMALLER the number actually is! 7

8 Concentration Calculation Practice Calculate the [OH ] at 25ºC when the [H + ] = 1.5 x 10-9 M, determine if the solution is acidic, basic, or neutral 1.0 x M = [OH ] [H + ] 1.0 x M = [OH ] [1.5 x 10-9 M] [OH ] = 6.67 x10-6 M The solution is basic [OH ] > [H + ] ph ph is a measure of how acidic or basic a solution is ph = log [H + ]; [H + ] = 10 ph Ex) ph water = log [1.0 x 10-7 M] = 7 Similarly, [H + ] water = 10 7 = 1.0 x 10-7 M need to know the [H + ] concentration to find ph ph An acid has a higher [H + ] than pure water, so its ph is < 7 A base has a lower [H 3 O + ] than pure water, so its ph is >7 8

9 ph the lower the ph, the more acidic the solution the higher the ph, the more basic the solution 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 ph can be negative (very acidic) or larger than 14 (very alkaline) ph of Common Substances Substance ph 1.0 M HCl 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 M NaOH 14 Other p Scales The p in ph tells us to take the negative log of the quantity (in this case, hydrogen ions). Some similar examples are poh = log [OH ] pk w = log K w 9

10 poh another way of expressing the acidity/basicity of a solution is poh poh = -log [OH ]; [OH ] = 10 -poh poh measures are the exact opposite of ph: poh < 7 is basic, poh > 7 is acidic poh = 7 is neutral Watch This! Because [H 3 O + ] [OH ] = K w = , we know that log [H 3 O + ] + log [OH ] = log K w = or, in other words, ph + poh = pk w = The Acid/ Base Square 10

11 Relationships: ph, poh, [H + ], [OH ] ph: [H + ]: H + H + H+ H + H+ OH OH - OH - OH - - OH - [OH - ]: poh: EQUATIONS TO REMEMBER! [H + ][OH ] = 1 x = k w ph = -log[h + ] [H + ] = 10 -ph poh = -log[oh - ] [OH ] = 10 -poh ph + poh = 14 How Do We Measure ph? For less accurate measurements, one can use Litmus paper Red paper turns blue above ~ph = 8 Blue paper turns red below ~ph = 5 An indicator 11

12 How Do We Measure ph? For more accurate measurements, one uses a ph meter, which measures the voltage in the solution. Strong You will recall that the seven strong acids are HCl, HBr, HI, HNO 3, H 2 SO 4, HClO 3, HClO 4. These are, by definition, strong electrolytes exist totally as ions in aqueous solution. For the monoprotic strong acids, [H 3 O + ] = [acid]. Strong Strong bases are the soluble hydroxides, which are the alkali metal heavier alkaline earth metal hydroxides (Ca 2+, Sr 2+, Ba 2+ ). Again, these substances dissociate completely in aqueous solution. 12

13 Dissociation Constants For a generalized acid dissociation, HA(aq) + H 2 O(l) A (aq) + H 3 O + (aq) the equilibrium expression would be K c = [H 3 O + ] [A ] [HA] This equilibrium constant is called the acid-dissociation constant, K a. Dissociation Constants The greater the value of K a, the stronger the acid. Calculating K a from the ph The ph of a 0.10 M solution of formic acid, HCOOH, at 25 C is Calculate K a for formic acid at this temperature. We know that K a = [H 3 O + ] [COO ] [HCOOH] 13

14 Calculating K a from the ph The ph of a 0.10 M solution of formic acid, HCOOH, at 25 C is Calculate K a for formic acid at this temperature. To calculate K a, we need the equilibrium concentrations of all three things. We can find [H 3 O + ], which is the same as [HCOO ], from the ph. Calculating K a from the ph ph = log [H 3 O + ] 2.38 = log [H 3 O + ] 2.38 = log [H 3 O + ] = 10 log [H3O+] = [H 3 O + ] = [H 3 O + ] = [HCOO ] Calculating K a from ph Now we can set up a table [HCOOH], M [H 3 O + ], M [HCOO ], M Initially Change At Equilibrium = =

15 Calculating K a from ph K a = [ ] [ ] [0.10] =

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