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Acids and Bases: Introductory Concepts

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1 Acids and Bases: Introductory Concepts
Arrhenius ...acids increase the ______ when dissolved in H2O. [H+] [OH–] ...bases increase the ______ when dissolved in H2O. e.g., HCl and NaOH -- useful concept, but limited to aq. solns. Svante Arrhenius (1859–1927)

2 Bronsted-Lowry acids: can transfer H+ to other substances (i.e., they
Johannes Bronsted (1879–1947) : Thomas Lowry (1874–1936) can transfer H+ to other substances (i.e., they are proton donors) Bronsted-Lowry bases: can accept H+ from other substances (i.e., they are proton acceptors) -- H+ and H3O+ are used interchangeably closer to reality; “hydronium ion” faster to write; “hydrogen ion” H+ H3O+ -- B-L concept is NOT limited to aqueous solutions

3 NH3(aq) + H2O(l) NH4+(aq) + OH–(aq)
Arrhenius and Bronsted-Lowry definitions overlap, in many cases. NH3(aq) + H2O(l) NH4+(aq) + OH–(aq) B-L base B-L acid Arrhenius Bronsted Lowry (accepts H+) (donates H+) A. base (causes [OH–] to ) One substance can’t be a Bronsted-Lowry acid unless... another simultaneously acts as a B-L base. -- the acid must be able to lose H+ -- the base must have a nonbonding pair of e– that can bind with the H+ [ ] + H+ H–N–H H : e.g., NH3 in above example

4 [ ] [ ] Amphoteric substances can be acids or bases,
depending on the reaction conditions. HCl(aq) + H2O(l) H3O+(aq) + Cl–(aq) B-L base NH3(aq) + H2O(l) NH4+(aq) + OH–(aq) B-L acid [ ] [ ] + NH3 is another example. When a B-L acid, it morphs into NH2– on the P side. “ “ “ base, “ “ “ NH4+ “ “ “ “ .

5 -- In acid-base equilibria, protons are donated in
forward and reverse reactions. -- The two substances in a conjugate acid-base pair differ by a H+... and the acid has an extra H+. HNO2(aq) + H2O(l) NO2–(aq) + H3O+(aq) base conj. acid CONJ. BASE ACID

6 -- Strong acids / bases easily / ____ H+.
donate accept -- Weak acids / bases do NOT easily / ____ H+. donate accept -- The stronger a/n acid / base, the weaker its conj. base / acid. In every acid-base rxn, the position of eq. favors the transfer of H+ from stronger acid to stronger base. weaker (conjugate) acid weaker (conjugate) base STRONGER ACID STRONGER BASE

7 The Autoionization of Water
In water, we constantly have (a little)... H2O(l) + H2O(l) H3O+(aq) + OH–(aq) Thus 25oC), the eq. const. for water is: Kw = [H3O+] [OH–] = [H+] [OH–] = 1.0 x 10–14 This equation is taken to be valid for pure water and for dilute aqueous 25oC. [H+] > [OH–] [H+] < [OH–] [H+] = [OH–] ACID BASE NEUTRAL

8 At 25oC, calculate the hydrogen ion concentration if
the hydroxide ion concentration is 2.7 x 10–4 M. Is this solution an acid or a base? [H+] [OH–] = 1.0 x 10–14 [H+] (2.7 x 10–4) = 1.0 x 10–14 [H+] = 3.7 x 10–11 M [H+] < [OH–] base

9 pH = –log [H3O+] = –log [H+]
The pH Scale Definition of pH... pH = –log [H3O+] = –log [H+] -- as [H+] / , pH / Soren Sorensen (1868–1939) : 0 ACID BASE 14 neutral A change of 1 pH unit means that [H+] (and [OH–]) has changed by a factor of ___. 10 A solution with pH 2 is how many times more acidic than one with pH 5? 1000X more acidic (i.e., 1000X less basic)

10 Especially in biochemical reactions, the rate law is
often dependent on the hydrogen ion concentration. If the rate is 1st order in [H+], then doubling [H+] would double the rate. -- Human blood pH is between 7.35 and 7.45. red blood cell white blood cell platelet Scanning electron microscope micrograph of ordinary blood.

11 Blueberries grow best in soil
** Significant figures rule for logarithms: # of sig. figs. in [ ] = # of decimal places in pH Find the pH if the hydronium ion concentration is 5.2 x 10–9 M. pH = –log [H3O+] = –log (5.2 x 10–9) = Find the pH if the hydroxide ion concentration is 3.9 x 10–10 M. Blueberries grow best in soil having a pH between 4.5 and 5.0. [H+] [OH–] = 1.0 x 10–14 3.9 x 10–10 So [H+] = 2.56 x 10–5 M pH = –log [H+] = –log (2.56 x 10–5) =

12 Other equations: pOH = –log [OH–] [OH–] = 10–pOH [H+] = 10–pH pH + pOH = 14 Find [H+] if the pH = 5.22. [H+] = 10–pH = 10–5.22 = x 10–6 M

13 acid-base indicators: chemicals whose color depends on pH
Measuring pH pH meter a pair of electrodes acid-base indicators: chemicals whose color depends on pH e.g., litmus, phenolphthalein, bromthymol blue, methyl red, methyl orange Bromthymol blue is yellow at pH < 6.0 and blue at pH > 7.6. pH paper is paper impregnated with mixtures of various indicators.

14 -- these are strong electro- lytes that exist entirely as
Strong Acids and Bases -- these are strong electro- lytes that exist entirely as ions in aqueous solution -- memorize the names and formulas of the seven strong acids... ...and the eight strong, hydroxide bases... hydrochloric, HCl hydrobromic, HBr hydroiodic, HI chloric, HClO3 perchloric, HClO4 nitric, HNO3 sulfuric, H2SO4 the hydroxides of... Li, Na, K, Rb, Cs, Ca, Sr, Ba “strong base cations”

15 Strong electrolytes are often written using a one-sided
arrow. e.g., HNO3(aq) H+(aq) NO3–(aq) Find the pH of a M perchloric acid solution. HClO4 H+ + ClO4– init. [ ] 0.012 final [ ] ~0 0.012 0.012 (“Who cares?”) pH = –log [H+] = –log (0.012) o o o o o p p p p p =

16 If a nitric acid solution has pH = 2.66,
find the solution’s concentration. [H+] = 10–pH = 10–2.66 = 2.2 x 10–3 M HNO3 H+ + NO3– So orig. [HNO3] was also 2.2 x 10–3 M. Equipment for the production of nitric acid, formerly part of a U.S. military munitions plant in Joliet, IL.

17 ** NOTE: Ca(OH)2, Sr(OH)2, and Ba(OH)2 are strong
electrolytes, but have limited solubilities. This means that if you put a big chunk of any of these into water, little of the chunk will dissolve, BUT the little that does dissolve will float around as X2+(aq) and OH–(aq), NOT as X(OH)2(aq). Barium hydroxide is used in the titration of weak acids, particularly organic acids, because a clear solution of Ba(OH)2 – unlike NaOH or KOH – will NOT contain any carbonates; carbonates would introduce errors into an analytical titration because the CO32– ion acts as a weak base.

18 Find the pH of a M solution of calcium hydroxide. Ca(OH)2 Ca OH– init. [ ] 0.0034 final [ ] ~0 0.0034 0.0068 (“w.c?”) pOH = –log [OH–] = –log (0.0068) = pH + pOH = 14 2.17 pH = 11.83

19 Metal oxides, hydrides, and nitrides (containing O2–,
H–, and N3–, respectively) also react with water to produce strongly basic solutions. e.g., -- O2–(aq) + H2O(l) OH–(aq) -- H–(aq) + H2O(l) H2(g) + OH–(aq) -- N3–(aq) + 3 H2O(l) NH3(aq) + 3 OH–(aq) OH!


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