1 Acids and Bases An Introduction David A Katz Department of Chemistry Pima Community College, Tucson, AZ, USA
2 Properties of Acids 1. Sour taste (examples: vinegar, citric acid, lemon juice) 2. Turns litmus from blue to red (also affects other indicators) 3. Reacts with metals to liberate H 2 4. Reacts with base losing its acid properties 5. Reacts with salts to give a new acid and a new salt 6. Conducts electricity (electrolyte)
3 Properties of Bases 1. Bitter taste (examples: baking soda, soap) 2. Turns litmus from red to blue (also affects other indicators best known is phenolphthalein) 3. Soapy feel 4. Reacts with acid losing its basic properties 5. Conducts electricity (electrolyte)
4 The Arrhenius Theory Svante August Arrhenius ( ) Acid: Substance that produces hydrogen ions in water solution. HCl (aq) H + (aq) + Cl (aq) Base: Substance that produces hydroxide ions in water solution. NaOH (aq) Na + (aq) + OH (aq) An acid neutralizes a base H + (aq) + OH (aq) H 2 O (l)
5 The Arrhenius Theory Acid strength depends on the amount of hydrogen ions produced. Definition includes acids such as HCl, HBr, HI, HNO 3, H 2 SO 4, HSO 4, HC 2 H 3 O 2, etc. Base strength depends on amount of hydroxide ions produced. Definition includes bases such as NaOH, KOH, Ca(OH) 2, Mg(OH) 2, Al(OH) 3, etc.
6 The Arrhenius Theory Problems with the Arrhenius Theory The solvent is limited to water, but water is not involved in the acid base reaction A solution of CO 2 in water is acidic, but H 2 CO 3 exists at a concentration less than 1% of the CO 2 A solution of NH 3 in water is basic, but NH 4 OH does not exist (Note: the formula NH 4 OH was invented by Arrhenius to explain the basic nature of NH 3 solutions) The reaction of HCl and NH 3 results in an acidic solution
7 A Generalized Arrhenius Theory The solvent (water) can ionize to produce H + and OH ions H 2 O (l) H + (aq) + OH (aq) Acid: Substance that increases the concentration of hydrogen ions in solution. HCl (aq) H + (aq) + Cl (aq) A strong acid is 100% dissociated A weak acid is only slightly dissociated
8 A Generalized Arrhenius Theory Base: Substance that increases the concentration of hydroxide ions in water solution. NaOH (aq) Na + (aq) + OH (aq) A strong base is 100% dissociated A weak base is only slightly dissociated Hydrolysis reactions can change H + and OH concentration in water solution CO 2 + H 2 O H + + HCO 3 CO 2 is an acid NH 3 + H 2 O NH 4+ + OH NH 3 is a base
9 A Generalized Arrhenius Theory Solvents other than water can be used: The solvent can ionize to produce positive and negative ions Example: liquid ammonia, NH 3 2 NH 3 NH 4+ + NH 2 Acid: Substance that increases the concentration of the positive ion in solution. HCl + NH 3 NH 4+ + Cl Base: Substance that increases the concentration of the negative ion in water solution. NaOH + NH 3 Na + + NH 2 + H 2 O (l)
10 A Generalized Arrhenius Theory Solvents other than water (continued) Neutralization produces the solvent: Example: In liquid ammonia, NH 3 NH 4+ + NH 2 2 NH 3
11 The Brønsted Lowry Theory Johannes Nicolaus Brønsted ( ) and Thomas Martin Lowry ( ) independently proposed the proton definition of acids and bases in 1923 Quoting Brønsted: "... acids and bases are substances that are capable of splitting off or taking up hydrogen ions, respectively. or An acid base reaction consists of the transfer of a proton (or hydrogen ion) from an acid to a base
12 The Brønsted Lowry Theory An acid is a proton donor That is, an acid is a substance from which a proton (H + ) can be removed. A Base is a proton acceptor That is, a base is a substance that has a nonbonded electron pair that can bond with a proton (H + ) from an acid. No solvent is specified
13 The Brønsted Lowry Theory If a substance can either lose a proton or gain a proton, then it is amphiprotic Some examples are HCO 3, HSO 4, and H 2 O Using HCO 3 : as an acid: HCO 3 + H 2 O H 3 O + + CO 3 2 as a base: HCO 3 + H 3 O + H 2 CO 3 + H 2 O Note that the proton (H + ) is combined with water forming H 3 O +
14 The Brønsted Lowry Theory HCl + H 2 O H 3 O + + Clˉ Looking at the forward reaction: HCl is an acid, because it has a proton available to be transferred. H 2 O is a base, since it bonds with the proton that the acid lost. Looking at the reverse reaction: H 3 O + is an acid, because it can give a proton to the Clˉ Clˉ is a base, since it can bond with the proton from H 3 O + Note that each pair HCl and Clˉ, and, H 2 O and H 3 O + differ by one proton. These pairs are called conjugate acid base pairs
15 The Brønsted Lowry Theory So, in the reaction: HCl + H 2 O H 3 O + + Clˉ Acid Base Conjugate Conjugate Acid Base One acid base conjugate pair is HCl and Cl HCl is an acid, and Clˉ is the conjugate base of HCl The second acid base conjugate pair is H 2 O and H 3 O H 2 O is a base, and H 3 O + is the conjugate acid of H 2 O
16 Conjugate Acids and Bases: From the Latin word conjugare, meaning to join together. Reactions between acids and bases always yield their conjugate bases and acids. Another example is:
17 Strong Acids HNO 3, HCl, H 2 SO 4 and HClO 4 are the most commonly known strong acids.
18 This is a submicroscopic artist s view Strong Acids
19 Weak Acids Weak acids are much less than 100% ionized in water (usually 5% ionic or less) One of the best known weak acids is acetic acid, CH 3 CO 2 H
20 Weak Acids
21 Strong Bases A Strong Base is 100% dissociated in water. NaOH (aq) Na + (aq) + OH (aq) Other common strong bases include KOH and Ca(OH) 2 CaO (lime) + H 2 O Ca(OH) 2 (slaked lime) CaO
22 Weak Bases A Weak base is less than 100% ionized in water One of the best known weak bases is ammonia NH 3(aq) + H 2 O (l) NH 4 + (aq) + OH (aq)
23 Weak Bases
24 Strong Acids The seven strong acids are HCl, HBr, HI, HNO 3, H 2 SO 4, HClO 3, and HClO 4. These are, by definition, strong electrolytes and exist totally as ions in aqueous solution (i.e.,they are 100% ionic in solution) For the monoprotic strong acids, the concentration of H 3 O + is equal to the concentration of the acid: [H 3 O + ] = [acid]
25 Strong Bases Strong bases are the soluble hydroxides, which are the alkali metal and heavier alkaline earth metal hydroxides (Ca 2+, Sr 2+, and Ba 2+ ). Strong bases dissociate completely in aqueous solution (i.e., they are 100% ionic in solution). For a monohydroxy strong base, the concentration of OH is equal to the concentration of the base: [OH ] = [base]
26 Weak Acids Acetic acid, HC 2 H 3 O 2, is a weak acid HC 2 H 3 O 2(aq) + H 2 O (l) H 3 O + (aq) + C 2 H 3 O 2 (aq) Acetate is a stronger base than H 2 O, so the molecular form (the left side of the equation) is favored. Only about 1% of the acetic acid is ionic.
27 Polyprotic Acids Have more than one ionizable H A common polyprotic acid is sulfuric acid, H 2 SO 4 The dissociation of a polyprotic acid is written to take place in steps: H 2 SO 4 (aq) + H 2 O (l) HSO 4 (aq) + H 3 O + (aq) HSO 4 (aq) + H 2 O (l) SO 4 2 (aq) + H 3 O + (aq) For a weak acid or weak base, all the ions shown in the equation are present in solution.
28 Polyprotic Acids
29 Polyprotic Acids
30 Autoionization of Water Water is amphoteric. In pure water, a few molecules act as bases and a few act as acids. H 2 O (l) + H 2 O (l) H 3 O + (aq) + OH (aq) This process is referred to as autoionization.
31 Autoionization of Water The product of the concentrations of H 3 O + and OH is given by the equation: K w = [H 3 O + ] [OH ] = 1.00 x at 25 o C In a neutral solution the concentrations [H 3 O + ] = [OH ] so [H 3 O + ] = [OH ] = 1.00 x 10 7 M
32 ph A common way to express acidity and basicity is with ph ph is defined as the negative logarithm (to the base 10) of the hydrogen ion (hydronium) concentration In a neutral solution, ph = log [H 3 O + ] [H 3 O + ] = [OH ] = 1.00 x 10 7 at 25 o C ph = log (1.00 x 10 7 ) = ( 7) = 7
33 ph Therefore, in pure water, ph = log ( ) = 7.00 An acid has a higher [H 3 O + ] than pure water, so its ph is <7 A base has a lower [H 3 O + ] than pure water, so its ph is >7.
34 ph The concept of ph was first introduced by Danish chemist Søren Peder Lauritz Sørensen ( ), the head of the Carlsberg Laboratory s Chemical Department, in 1909 Dr. Sørensen developed the ph scale during his pioneering research into proteins, amino acids and enzymes the basis of today s protein chemistry in a paper titled Enzyme Studies II. The Measurement and Meaning of Hydrogen Ion Concentration in Enzymatic Processes : The value of the hydrogen ion concentration will accordingly be expressed by the hydrogen ion based on the normality factor of the solution used, and this factor will have the form of a negative power of 10. Since in the following section I usually refer to this, I will explain here that I use the name "hydrogen ion exponent" and the designation P H for the numerical value of the exponents of this power. Sørensen and the Carlsberg Chemistry Department
35 ph Today, we refer to ph as meaning the power of hydrogen. The ph scale provides a simple and universal measurement of the amount of hydrogen ions in a solution, which affects its acidity and how it reacts chemically. Each value of ph means the H + concentration changes by a factor of 10 As the H + concentration decreases, the OH concentration increases ph 1 ph 7 ph 14 strong weak neutral acid acid weak strong base base The ph scale according to the late Dr. Hubert Alyea, Princeton University
36 ph values for some common substances
37 The Leveling Effect The ph scale ranges from 0 to 14 Can an acid or base have a ph lower than 0 or higher than 14? When a strong acid, such as HCl, is dissolved in water, it reacts to form H 3 O + in the following reaction: HCl (aq) + H 2 O (l) H 3 O + (aq) + Cl (aq) Any acid that is stronger than H 3 O + reacts with H 2 O to form H 3 O + ; therefore, no acid can be stronger than H 3 O + in H 2 O.
38 The Leveling Effect In the same way, a base which is stronger than the conjugate base of water, such as sodium oxide, will react with water to give the weaker base which is the hydroxide ion, OH : Na 2 O (s) + H 2 O 2OH (aq) + 2Na + (aq) Note: The actual base here is the oxide ion since the sodium ion is an extremely weak acid or base. All bases which are stronger than the hydroxide ion will react with water to produce hydroxide ion. Although oxide ion, amide ion, ethoxide ion, and methoxide ion are all stronger bases than hydroxide ion, their strength in aqueous solution is leveled to that of hydroxide ion. Any base that is stronger than OH reacts with H 2 O to form OH ; therefore, no base can be stronger than OH in H 2 O.
39 The Leveling Effect Can the strengths of strong acids or bases can be differentiated? The leveling effect operates in any protonic solvent. If a solvent other than water is used, differences between strengths of strong acids or bases can be measured. In liquid ammonia, for example, all acids are levelled to the strength of the ammonium ion, NH 4+, and all bases are leveled to the strength of the amide ion, NH 2. 2 NH 3 NH 4+ + NH 2 Many of the acids which are weak in water act as strong acids in liquid ammonia because they are stronger than ammonium ion. Not all of the bases which are strong in water are also strong in liquid ammonia.
40 The Leveling Effect Glacial acetic acid is another protonic solvent in which the leveling effect takes place. HC 2 H 3 O 2 H + + C 2 H 3 O 2 Glacial acetic acid can be used to show that hydrogen chloride is a weaker acid than is perchloric acid, since hydrogen chloride behaves as a weak acid in glacial acetic acid. Methanol is also a protonic solvent in which some of the acids which are strong (completely dissociated) in water are found partially in molecular form
41 ph and poh Previous we saw: [H 3 O + ] [OH ] = K w = If we take the negative log of [H 3 O + ] and [OH ] log [H 3 O + ] + log [OH ] = log K w = or, in other words, ph + poh = pk w = 14.00
42 Measuring ph For a simple acid or base determination we use an indicator known as Litmus paper Litmus is a water soluble mixture of different dyes extracted from lichens, especially Roccella tinctoria. The name litmus comes from Middle English litemose (of Scandinavian origin; akin to Old Norse litmosi, dyer's herbs : litr, color, dye + mosi, bog, moss) and Middle English lykemose (from Middle Dutch lijkmoes, variant of lēcmoes : lēken, to drip + moes, moss). Red litmus paper turns blue above ~ph = 8 Blue litmus paper turns red below ~ph = 5
43 Measuring ph ph test papers are made using a mixture of dyes to indicate ph values over a wide range or, for more accurate measurements, there are short range papers.
44 Measuring ph Indicators are dyes or mixtures of dyes that can be added to solutions of acids or bases to determine ph. Some common indicators and their color changes are shown in the chart below:
45 Measuring ph For more accurate measurements, a ph meter is used. Using special glass electrodes, the meter measures the voltage of the solution as a function of the activity of the hydrogen ions near the tip of the electrode.
46 The ph Meter First ph meter was constructed in 1934 by Arnold Beckman ( ). A glass ph electrode that had a potential dependent on activity of H + ions had been constructed in 1906 by Fritz Haber and Zygmunt Klemensiewicz, but there were technical difficulties due to a large internal resistance of glass electrodes. To obtain reliable results one was forced to use very sensitive galvanoscope expensive and difficult to maintain. To overcome the problem Arnold Beckman proposed to use simple high gain amplifier made using two vacuum tubes. Amplified current was much easier to measure with cheap miliamperometers. Beckman s first ph meter, 1934 (middle photo) The Model G ph meter, the first successful marketed ph meter, 1936 (bottom photo)
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