Notes Acids and Bases

Arrhenius Acid Base Theory:

In 1884 Svante Arrhenius proposed the first theoretical model for acids and bases. Prior to that time, these chemically opposite substances were described in properties such as their taste; their effects on metals, carbonates, and dyes (called indicators); their feel to the touch, and their ability to react with each other. According to the Arrhenius theory, pure water dissociates to some extent to produce hydrogen ions, H+ and hydroxide ions, OH-. When this occurs, equal amounts of H+ and OH- ions are produced: H2O(l) H+(aq) + OH-(aq) An acid, according to Arrhenius, is any substance that liberates H + ions when placed in water. When the H+ concentration is elevated the OH- concentration decreases, this solution is said to be acidic. Similarly, a base is defined as any substance that liberates OH - ions when placed in water. The resulting solution has a higher concentration of OH - ions than H+ ions and is said to be basic, or alkaline. ACID: BASE: HCl(aq) H+(aq) + Cl-(aq) NaOH(aq) Na+(aq) + OH-(aq)

Brnsted - Lowry Acid Base Theory:

A more general and realistic theory was proposed by two chemists working independent of the other, Johannes Nicolaus Brnsted of Denmark and Thomas Martin Lowry of England. Both chemists are given credit; the theory is named the Brnsted-Lowry theory. Acids are defined as substances that donate H+ ions, protons and therefore are called proton donators, while bases are substances that accept protons and are defined as proton acceptors. On this basis, the autoionization of water is given as follows: H2O(l) + H2O(l) H3O+(aq) + OH-(aq) In this reaction, one water molecule donates a proton, H +, and behaves as an acid, while the other water molecule accepts the proton and behaves as a base. Since the reaction is written reversible, we see that when it proceeds from right to left, the hydronium ion, H3O+ behaves as an acid, a proton donor while the hydroxide ion, OH - behaves as a base, a proton acceptor. This theory is considered more realistic because the proton would not wander around in an aqueous solution by its lonesome. The lone pairs of electrons of the oxygen in water would instantly bond with the proton to produce a hydronium ion. Arrheniuss theory did not take this into account. Nitric acid, HNO3 behaves as a typical Brnsted-Lowry acid in water solution: HNO3(aq) + H2O(l) H3O+(aq) + NO3-(aq) 1

We see that according to this reaction, HNO 3 added to water generates H3O+ ions in solution. This causes the solution to contain more H3O+ than OH- thus the solution is acidic. Similarly, a base such as ammonia, NH3 accepts a proton from water, thus generating OH - ions and the solution is basic:
H H N H H O H H H N H H OH
-

The strength of an acid or base is a measurement of the extent to which reactions such as the two above react. A strong acid or base is said to dissociate 100%. For example HCl, hydrochloric acid dissociates fully into H+ and Cl- ions. But as discussed earlier the H+ will not persist in the solution. It will combine with water to form the H 3O+, hydronium ion. There are no HCl molecules left; they have all separated. The same goes for strong bases like the sodium hydroxide, NaOH. There will not be any NaOH left, as it will all be dissolved into Na + and OHions. HCl(aq) + H2O(l) H3O+(aq) + Cl (aq) NaOH(aq) Na+(aq) + OH-(aq) Again, the reaction of HCl takes place almost completely. So, a 2.0 Molar HCl solution produces 2.0 Molar H3O+ and 2.0 Molar Cl- ions when dissolved in water. Thus, hydrochloric acid is classified as a strong acid. On the other hand, the reaction of ammonia, NH 3 to form the NH4+ ion does not take place completely. Most of the ammonia remains in the form of NH 3 molecules. Thus, 2.0 Molar NH3 dissolved in water produces less than 2.0 Molar NH 4+ and less than 2.0 Molar OH- ions. Because of this, ammonia is called a weak base.

Lewis Acid Base Theory:

I hate to tell you this but there is a more general, slightly more recent theory of acids and bases, the Lewis acid base theory. Gilbert Newton Lewis is one of the great chemists in history. His greatest discovery may well be the theory of the covalent bond in 1916, but he made many other contributions. One was his theory of acids and bases. In 1923, he wrote: "We are so habituated to the use of water as a solvent, and our data are so frequently limited to those obtained in aqueous solutions, that we frequently define an acid or a base as a substance whose aqueous solution gives, respectively, a higher concentration of hydrogen ion or of hydroxide ion than that furnished by pure water. This is a very one sided definition . . . ." What Lewis wanted was a general definition of an acid and a base, one that was universal no matter what the chemical environment. He knew that the current ideas (the Arrhenius theory dating from the late 1800's and the Brnsted-Lowry theory - announced in January 1923) were not sufficient. In the next 2 pages of discussion, after the above quote, Lewis wrote:

"When we discuss aqueous solutions of substances which do not contain hydroxyl [ion], it is simplest to define a base as a substance which adds hydrogen ion. . . . Since hydrogen is a constituent of most of our electrolytic solvents, the definition of an acid or base as a substance which gives up or takes up hydrogen ion would be more general than the one we used before, but it would not be universal." Lewis then gives his definition of an acid and a base: "We are inclined to think of substances as possessing acid or basic properties, without having a particular solvent in mind. It seems to me that with complete generality we may say that a basic substance is one which has a lone pair of electrons which may be used to complete the stable group of another atom, and that an acid is one which can employ a lone pair from another molecule in completing the stable group of one of its own atoms." By the way, this is a quot from Lewis'. He finished the above paragraph with one more sentence, a restatement of what he just said: "In other words, the basic substance furnishes a pair of electrons for a chemical bond, the acid substance accepts such a pair." It is important to make two points here: NO hydrogen ion need be involved. NO solvent need be involved. The Lewis theory of acids and bases is more general than the "one sided" nature of the Brnsted-Lowry theory. Keep in mind that Brnsted-Lowry, which defines an acid as a proton donor and a base as a proton acceptor, REQUIRES the presence of a solvent, specifically a protic solvent, of which water is the usual example. Since almost all chemistry is done in water, the fact that this limits the Brnsted-Lowry definition is of little practical consequence. The Lewis definitions of acid and base do not have the constraints that the Brnsted-Lowry theory does and, as we shall see, many more reactions were seen to be acid base in nature using the Lewis definition than when using the Brnsted-Lowry definitions. To recap, a Lewis acids and bases are defined as: Acid: an electron acceptor. Base: an electron donor. A "Lewis acid" is any atom, ion, or molecule that can accept electrons and a Lewis base is any atom, ion, or molecule capable of donating electrons. You may read donating or accepting an electron pair. This is not always the case; it could be a single electron. It turns out that it may be more accurate to say that Lewis acids are substances which are electron deficient or low electron density and Lewis bases are substances which are electron rich or high electron density. Examples of Lewis acids: positive ions having less than a full octet in the valence shell polar double bonds (one end) expandable valence shells

Examples of Lewis bases: 3

negative ions one of more unshared pairs in the valence shell

polar double bonds (the other end) the presence of a double bond

Properties of Acids:
Produce H3O+ ions in water Turns litmus from blue to red Sour taste Double Replacement with solid oxides o turns rusting metals into salts Double Replacement with hydroxides o neutralizes bases o always forms a salt and water Double Replacement with carbonates and bicarbonates o turns carbonates into salts and CO2 o antacids in your stomach remove acid Liberate H2(g) from water in a redox reaction with a metal. o this is a part of the activity series for metals o drop a metal in an acid and you might get H 2, check the activity series

Look at the net ionic from one of these reactions to see that any acid will do for each of these reactions: (always forms a salt and water)

2 HCl(aq) + Ca(OH)2(aq) CaCl2(aq) + 2 H2O(l) H+(aq) + OH- (aq) 2 H2O(l)

Cl-(aq) is removed in the net ionic equation, meaning an ion of the acid would do Br -, I-, NO3- etc Different acids have different possible molarities, for the most concentrated solution they will make. HCl 12 M HNO3 16 M H2SO4 18 M CH3COOH 18 M

Properties of Bases:
Produces OH- in water Turns litmus from red to blue Slippery feeling Bitter taste Neutralizes acidic solutions o always forms a salt and water Breaks down fats and oils o which is why many house hold cleaners are basic 4

Will produce soap from fats or oils if heated

Properties Salts:
Product of an acid-base reaction Many are soluble o for this reason most drugs are a salt, most specifically sodium o this gets the drug into the bloodstream as all sodium compounds are soluble o if a drug cannot be turned into a salt it will not dissolve in water and is useless to a patient as it will not enter the bloodstream Ionic compounds Salts of weak acid and bases are used to form buffers Hydroscopic: they absorb water very well to form hydrates o CaSO4 2H2O Gypsum

The list of strong acids include: HCl, HBr, HI, HNO3, H2SO4, HClO3 and HClO4. The list of strong bases include: LiOH, NaOH, KOH, RbOH and CsOH. What do the strong bases have in common? They are all composed of a group one metal and a hydroxide. From the solubility rules all compounds containing a group one metal are soluble. All of these acids and bases dissociate 100% in water. Example of strong acid in water: HCl(aq) + H2O(l) H3O+(aq) + Cl (aq) Example of a strong base in water: NaOH(aq) + H3O+(aq) Na+(aq) + 2 H2O(l) Example of weak acid in water: HF(aq) + H2O(l) H3O+(aq) + F (aq) conjugat conjugate acid + base e acid base Websters Definitions of Conjugate: 1 a: joined together, especially in pairs 1 b: acting or operating as if joined 2 a: having features in common but opposite or inverse in some particular The strong and weak reactions look the same, with one very important distinction the and The reactions with strong acids and bases go one way; they do not reform the reactants. The reactions with weak acids and bases go both ways, they will form an equilibrium according to their K value and the temperature. The K value is really a measure of the degree to which the acid or base are ionized. If a K value for an acid is low, like .00000378, then not many of the hydrogens separate from the acid. K values are given subscripts for the various substances they are describing. The K for an acid is a Ka and the K for a base is Kb. Problem: Write the equilibrium expression for the above weak acid and base reactions. 5

Ka =

[H 3O + ][F ] = 7.2 x10 4 [ HF]

[Ca +2 ] Kb = = 5.5x10 6 + [ Ca (OH) 2 ] H 3O Tums are made of calcium hydroxide. They do not burn your mouth or throat because they will not dissociate in your mouth or throat, they are insoluble unless in an acid solution, your stomach.

The K values for these get special subscripts, Ka and Kb, for acid and base, obviously.

Auto-Ionization of Water:

H2O H+ + OHThe equilibrium equation is as follows:

K w = H + OH

[ ][

The following is not how you will see the equilibrium written. H 2O is a pure liquid and like solids, pure liquids are not included in the equilibrium equation. The equilibrium is written in terms of moles per liter. Solids and pure liquids are not described by these units.

Kw =

[ H + ][OH ] [ H 2O ]

The K value for this is 1 x 10-14 and is referred to as Kw. This means only 1 out of every 100,000,000,000,000 water molecules breaks down. This number will be revisited when we get to acids and bases. The Kw will not change. It is set even if you change the [H +] or [OH-]. So, if you add an acid and increase the [H+] and the Kw value stays the same, then the [OH-] must go down. Here is a table of this relationship.

How pH relates [H+], [OH-] and Kw

[H+] [OH-] Kw pH = 100 10-1 10-2 10-3 10-4 10-5 10-9 10-6 10-8 10-7 10-7 10-8 10-6 10-9 10-5 10-10 10-11 10-12 10-13 10-14 10-4 10-3 10-2 10-1 100 10-15 101 10-14 15

= 10-14 10-13 10-12 10-11 10-10

= 10-14 10-14 10-14 10-14 10-14 10-14 10-14 10-14 10-14 10-14 10-14 10-14 10-14 10-14 10-14 =. 0 1 2 3 4 5 6 7 8 9 10 11 12 13 14

Table shows that at 25oC the product [H+] x [OH-] always must equal 1 x 10-14
If you look at this table you see a relationship between K w, Ka and Kb.

Kw = Ka x Kb
6

So, if you know a Ka you can calculate the Kb because Kw is always 1 x 10-14. And if you know a Kb you can calculate the Ka because Kw is always 1 x 10-14 pH is used to describe the acidic or basic nature of a solution. The H in pH means the concentration of hydrogen ion, H+ in a solution. The p in pH is just a mathematical trick to make a decimal number a whole number. People do not like decimals and do not like exponents and really hate negative exponents. The p in pH is log. Again, the H in pH is the concentration of H+ in molarity, but since it is in water we really mean hydronium, [H 3O+]. To get the pH from the [H+], the [brackets] mean concentration in molarity or moles per liter, take the log of the concentration and the multiple the answer by negative 1. If the concentration of [H+] or [H3O+] is .0001 M, the pH can be calculated by taking the log of this number and multiplying by negative 1. The number .0001 M can be converted to scientific notation; it takes the form 1 x 10-4. log(1 x 10-4) = -4 4 x -1 = 4 pH = 4 If the concentration of [H+] or [H3O+] is 8.3 x 10-9 M, the pH can be calculated by taking the log of this number and multiplying by negative 1. log(8.3 x 10-9) = -8.08 1 x -8.08 = 8.08 pH = 8.08
K = H + OH
-14

1 x 10 = X X 1 x 10-14 = X2
1x10 14 = X 2

[ ][

1 x 10-7 = X [H+] = 1 x 10-7 pH = 7 pH is related to pOH through the Kw of water: pH + pOH = 14

pH of Common Compounds:

Here is a list of strong acid and bases and their K a and Kb values.

BASE alanine ammonia dimethylamine ethylamine glycine hydrazine methylamine trimethylamine

FORMULA C3H5O2NH2 NH3 (CH3)2NH C2H5NH2 C2H3O2NH2 N2H4 CH3NH2 (CH3)3N

kB 7.41 x 10-5 1.78 x 10-5 4.79 x 10-4 5.01 x 10-4 6.03 x 10-5 1.26 x 10-6 4.27 x 10-4 6.31 x 10-5

pkB 4.13 4.75 3.32 3.30 4.22 5.90 3.37 4.20

Here is a list of the Ka values from a few weak acids.

ACID acetic acid ascorbic acid (1) ascorbic acid (2) boric acid (1) boric acid (2) boric acid (3) butanoic acid carbonic acid (1) carbonic acid (2) chromic acid (1) chromic acid (2) citric acid (1) citric acid (2) citric acid (3) formic acid heptanoic acid hexanoic acid hydrocyanic acid hydrofluoric acid lactic acid nitrous acid octanoic acid oxalic acid (1) oxalic acid (2) pentanoic acid phosphoric acid (1) phosphoric acid (2) phosphoric acid (3) propanoic acid sulfuric acid (2) sulfurous acid (1) sulfurous acid (2) uric acid FORMULA H(C2H3O2) H(HC6H6O6) H(C6H6O6) H(H2BO3) H(HBO3)H(BO3)-2 H(C4H7O2) H(HCO3) H(CO3)H(HCrO4) H(CrO4)
-

Ka 1.74 X 10-5 7.94 X 10-5 1.62 X 10 5.37 X 10

-12 -10

pKa 4.76 4.10 11.79 9.27 12.7 13.8 4.83 6.35 10.33 0.74 6.49 3.14 4.77 6.39 3.75 4.89 4.84 9.21 3.20 3.08 3.25 4.89 1.23 4.19 4.84 2.16 7.21 12.32 4.86 1.98 1.85 7.20 3.89

pKa is like pH p = negative log so pKa = -1 x log(ka)

1.8 X 10-13 1.6 X 10-14 1.48 X 10-5 4.47 X 10 1.82 X 10 3.24 X 10

-7

4.68 X 10-11
-1 -7

H(H2C6H5O7) H(HC6H5O7) H(C6H5O7) H(CHO2) H(C7H13O2) H(C6H11O2) HCN HF H(C3H5O3) HNO2 H(C8H15O2) H(HC2O4) H(C2O4)
-2

7.24 X 10-4 1.70 X 10 4.07 X 10 1.78 X 10 1.41 X 10 6.31 X 10 8.32 X 10 1.29 X 10 5.89 X 10 6.46 X 10 6.92 X 10 6.17 X 10 1.38 X 10 1.05 X 10 6.31 X 10 1.29 X 10
-5 -7 -4

1.29 X 10-5
-5

6.17 X 10-10
-4 -4

5.62 X 10-4
-4 -2 -5

H(C5H9O2) H(H2PO4) H(HPO4) HPO4-2 H(C3H5O2) HSO HSO

4 -

3.31 X 10-5
-3 -8

2.09 X 10-12
-5 -2

H(HSO3)
3

1.41 X 10-2
-8 -4

H(C5H3N4O3)

Salts are compounds composed of a metal and a non-metal. Normally, this is composed of one component from the left side of the periodic table and one component from the right side. The left side of the table is filled with metal, metal atoms give up electrons and therefore become positively charged ions. Positively charged ions are named cations. The right side of the periodic table, those elements to the right of the stair-steps formed by the metalloids, are considered non-metals. Non-metal atoms gain electrons in ionic compounds and therefore become negatively charged ions. Negatively charged ions are named anions. An interesting phenomenon occurs when certain salts dissociate in an aqueous solution, the pH may change. If the cation and anion of which this salt is composed are the cations and anions from strong acids and bases the pH of the solution does not change. NaCl is composed of the cation Na+ and the anion Cl-. If an H+ is added to the Cl- you get hydrochloric acid. Will this HCl molecule form in this aqueous environment? No, as HCl is a strong acid and strong acids dissociate 100% so you cannot have an HCl molecule in water. If an OH - is added to the Na+ from the salt, will a NaOH molecule form? No, as NaOH is a strong base and strong bases dissociate 100%, so you cannot have a NaOH molecule in water. What salts will the pH change? Salts of weak acid and weak bases will have a pH change. There are way too many weak acids and bases to list, if you remember all the strong acids and bases, then all the other millions of acid and bases in the world will be weak. So, an acid like HF, hydrofluoric acid is a weak acid. If a salt is made with the anion of that weak acid, that salt will be able to change the pH of a solution. NaF(aq) F-(aq) + H2O(l) Na+(aq) HF(aq) + + F-(aq) OH-(aq)

The above two equations show the dissociation of a salt and the basic properties of the anion of a weak acid. The fluoride ion is a base as it takes an H + ion from the water. The reaction of a salt changing pH is called acid-base hydrolysis. The name is derived from what happens in the reaction. A water molecule is broken, hydro = water and lysis = breaking. In general, the anions of weak acids behave as bases, while the anions of strong acids do not. Similarly, the cations of weak bases behave as acids, while the cations of strong bases do not. The term neutralization is often used to describe a reaction in which equal amounts of acid and base react with each other. Acid and bases can react with some compounds to change their color. These compounds are dyes that change color as the pH changes and are referred to as indicators. This is one method used to determine the point at which exact amounts of acid and base have been reacted in neutralization reactions. Normally, the products of the reaction are water and salt. The salt follows the rule of solubility and will either dissolve or not depending on what salt if formed. Thus, the neutralization of nitric acid with potassium hydroxide is represented by the following reaction: HNO3(aq) + KOH(aq) H2O(l) + K+(aq) + NO3-(aq) The potassium ion and nitrate ion are dissociated from each other as; all compounds containing a group one metal are always soluble. Also, all compounds containing nitrates are soluble. So, 10

this compound is very soluble, neither ion wants to form a solid in water. The products of this reaction could be duplicated by simply adding the salt potassium nitrate to a container of water. To determine which salts will dissolve and which will remain as a solid molecule, consult a table of the rules of solubility. Solutions containing substances with the ability to donate protons and substances with the ability to accept protons have the capacity to maintain a fairly constant pH despite the addition of acids or bases. Solutions with this capacity are called buffers, and the amount of acid or base they can accept without significant change is called the buffer capacity. A common type of buffer consists of a solution containing about equal amounts of a weak acid and the salt anion of the weak acid. Formic acid (HCHO2) and its salt, sodium formate (NaCHO2) could be used. Formic acid reacts with water as follows: HCHO2(aq) + H2O(l) H3O+(aq) + CHO2-(aq) Thus HCHO2 behaves as a Brnsted acid, while CHO2- would behave as a Brnsted base. In a solution containing both species, the addition of acid, H + would not change the pH much because the CHO2- ions would react as follows to minimize the formation of H 3O+: CHO2-(aq) + H+(aq) (from added acid) HCHO2(aq) Looking at this reaction we see that an acid was added to the solution but there is not a hydronium ion on the product side. This means the pH did not change because there is no more hydronium in the solution than there was before the acid was added. This is the function of a buffer. A substance that should have added H+ to a solution has those H+ consumed by buffer, thereby not increasing the amount of H + in the solution. Similarly, any added base will deplete the H 3O+ concentration, but the HCHO2 molecules present will replenish them by undergoing the reaction from left to right in the below equation. HCHO2(aq) + H2O(l) H3O+(aq) + CHO2-(aq)

11

Buffers:
As you have seen in calculating the pH of solutions, only a small amount of a strong acid is necessary to drastically alter the pH. For certain experiments, however, it is desirable to keep a fairly constant pH while acids or bases are added to the solution either by reaction or by the experimenter. Buffers are designed to fill that role. Chemists use buffers routinely to moderate the pH of a reaction. Biology finds manifold uses for buffers, which range from controlling blood pH to ensuring that urine does not reach painfully acidic levels. A buffer is simply a mixture of a weak acid and its conjugate base or a weak base and its conjugate acid. Buffers work by reacting with any added acid or base to control the pH. For example, let's consider the action of a buffer composed of the weak base ammonia, NH 3, and its conjugate acid, NH4+. When HCl is added to that buffer, the NH3 "soaks up" the acid's proton to become NH4+. Because that proton is locked up in the ammonium ion, it proton does not serve to significantly increase the pH of the solution. When NaOH is added to the same buffer, the ammonium ion donates a proton to the base to become ammonia and water. Here the buffer also serves to neutralize the base. As the above example shows, a buffer works by replacing a strong acid or base with a weak one. The strong acid's proton is replaced by ammonium ion, a weak acid. The strong base OHwas replaced by the weak base ammonia. These replacements of strong acids and bases for weaker ones give buffers their extraordinary ability to moderate pH. Buffers are solutions that oppose a change in pH. Add either an acid or a base that equilibrium shifts to oppose a change in pH. Buffers are made with the salts of weak acids or weak bases. What happens when you put Na2CO3 into water? o It breaks up and CO3-2 is flowing in the water. What does it do? o It grabs hydrogens off of water until the equilibrium for carbonic acid is reached. So you can make a buffer with a weak acid and a salt of its conjugate base or a weak base and the salt of its conjugate acid. B pH = pK a + log [HB]

[ ]

12

Calculating the pH of Buffered Solutions:

Buffers must be chosen for the appropriate pH range that they are called on to control. The pH range of a buffered solution is given by the Henderson- Hasselbalch equation. For the purpose of the derivation, we will imagine a buffer composed of an acid, HA, and its conjugate base, A -. We know that the acid dissociation constant pKa of the acid is given by this expression:
Ka =

[H ][A ]
+ -

[ HA ]
a

The equation can be rearranged as follows

Taking the -log of this expression and rearranging the terms to make each one positive gives the Henderson-Hasselbalch equation: (taking the negative log of the ratio will give you acid on top and base on top, but H-H changed the sign, when taking logs, changing the sign causes the ratio to invert, as shown below) [ salt of conjugate base added] pH = pK a + log [ acid added] [ base] pH = pK a + log [ acid ] Note that the sample species HA and A- in the above expression are generalized to the terms acid and base, respectively. To use the equation, place the concentration of the acidic buffer species where the equation says "acid" and place the concentration of the basic buffer species where the equation calls for "base". It is essential that you use the pKa of the acidic species and not the pKb of the basic species when working with basic buffers --many students forget this point when doing buffer problems. A buffer problem can be fairly simple to solve, if you keep it simple. For example, to calculate the pH of a buffer solution that is 0.75 M acetic acid and 0.5 M sodium acetate the HendersonHasselbalch equation is used. You should recognize that this is a buffer solution because a weak acid and a salt of its conjugate base have been mixed in a solution. [ base] pH = pK a + log [ acid ]
[ 0.5M ] pH = 4.75 + log [ 0.75M ]

] [H ] = K [[HA A ]
+ -

pH = 4.57 This part of the problem does not require us to do the sort of equilibrium calculations that we must use for Non-Buffered Solutions. Now if we were to add 0.1 mol nitric acid, what would happen to the solutions pH? To calculate the pH we assume that the acid reacts with the base in solution and that the reaction has a 100% yield. Therefore, we say that 0.1 moles acetate ion reacts with 0.1 moles of nitric acid to give 0.1 moles of acetic acid and aqueous sodium nitrate. So, the final concentration of acetic acid is 0.85 M and acetate is 0.4 M. Plugging those values into the Henderson-Hasselbalch 13

equation gives a pH of 4.42. Note that a 0.1 M solution of strong acid would give a pH of 1 but the buffer gives a pH of 4.42 instead. See the calculations below to verify this difference. Calculation of pH after addition of 0.1 mol of nitric acid to buffer solution: [ 0.4M ] pH = 4.75 + log [ 0.85M ] pH=4.42 Calculations of pH after addition of 0.1 mol of nitric acid to non-buffered solution: pH = -log[H+] pH = -log[0.1M] pH = 1 If 40 mL of 0.25M NaOH is added to 550 mL of the water, what is the resultant pH? An acetic acid buffer solution has the following concentrations: [CH3COOH]=0.36M [CH3COO-]=0.32M If 40 mL of 0.25M NaOH is added to 550 mL of the buffer, what is the resultant pH? A propanoic acid buffer solution has the following concentrations: [C3H6O2]=0.55M [C3H5O2-]=0.23M If 10 mL of 0.2M HCl is added to 250 mL of the buffer, what is the resultant pH? A acrylic acid buffer solution has the following concentrations: pKa = 4.25 [C3H4O2]=0.6M [C3H3O2-]=0.25M If 50 mL of 0.2M NaOH is added to 600 mL of the buffer, what is the resultant pH?

pH of blood is regulated by several processes, CO2 intake and bicarbonate removal are one portion of the over all process. Here are the individual reactions:

CO2(g) CO2(aq)
14

CO2(aq) + H2O(l) H2CO3(aq) H2CO3(aq) + H2O(l) HCO3-(aq) + H3O+(aq)

We can combine them into an overall reaction, as shown below.

Polyprotic Acids:
Acids are said to be protic, which means they donate protons or hydrogen ions. Some acids can give more than one proton to a solution. The red hydrogen atoms are the acidic protons on the following molecules. Phosphoric is said to be triprotic as it can donate 3 acidic protons. Carbonic and phosphorous acids are said to be diprotic as they can donate 2 acidic protons. Nitric acid is said to be monoprotic as it can only donate one acid proton.
O H O P O H O H phosphoric acid O O N O H nitric acid phosphorous acid O H O C O H carbonic acid O H O P O H H

monoprotic one acidic hydrogen diprotic two acidic hydrogens triprotic three acidic hydrogens H3PO4 a triprotic acid. The first hydrogen is fairly easy to pull off, the second is difficult and the third is extremely difficult. phosphoric acid (1) H3PO4 phosphoric acid (2) H2PO4Ka1 = 6.92 x 10-3 Ka2 = 6.17 x 10-8 pKa = 2.16 pKa = 7.21 15

phosphoric acid (3) HPO4-2

Ka3 = 2.09 x 10-12

pKa = 12.13

Reactions Real World:

Acids and bases can react with many different substances. The extent and rate of such reactions often depends on the strength of the acids or bases involved. In some instances, the reactions are considered to be useful, as in the use of hydrofluoric acid to etch glass. In other cases, the reactions are undesirable, as in the deterioration of stone statues and buildings by acid rain formed from air pollutants.

SiO2(s)
glass not soluble in water

HF(aq)
hydrofluoric acid

H2SiF6(aq)
soluble in water

+ H2O(l)
water

CaCO3(s)
marble not soluble in water

H2SO4(aq)
sulfuric acid acid rain

CaSO4(aq)
soluble in water

+ H2O(l) +
water

CO2(g)
carbon dioxide

Titrations:
Titration is a general class of experiment where a known property of one solution is used to infer an unknown property of another solution. In acid-base chemistry, we often use titration to determine the pH of a certain solution.

Method of determining the concentration of an acid or basic solution. If you have a solution of unknown concentration and you want to know what the concentration is you do a titration. 1. Touch solution with litmus to determine if it is acidic or basic 2. Take a know volume of the unknown and put it into a flask 3. Put a neutralizing solution of known concentration into a buret 4. Add an indicator to the unknown 16

5. Add the neutralizing solution until the indicator changes color 6. Record the volume of the neutralizing solution used That is all there is to the experimental portion. Be sure you do not go past the neutralization point. This point is termed the equivalence point, the point where the molecules of H 3O+ = the molecules of OH-.

Here is a little more in depth explanation. We use this instrumentation to calculate the amount of unknown acid in the receiving flask by measuring the amount of base, or titrant, it takes to neutralize the acid. There are two major ways to know when the solution has been neutralized. The first method uses a pH meter in the receiving flask, adding base slowly until the pH reads exactly 7. The second method uses an indicator. An indicator is an acid or base whose conjugate acid or conjugate base has a color different from that of the original compound. The color changes when the solution contains a 1:1 mixture of the differently colored forms of the indicator. As you know from the Henderson-Hasselbalch equation, the pH equals the pKa of the indicator at the endpoint of the indicator. Since we know the pH of the solution and the volume of titrant added, we can then deduce how much base was needed to neutralize the unknown sample. A titration curve is drawn by plotting data attained during a titration, titrant volume on the x-axis and pH on the y-axis. The titration curve serves to profile the unknown solution. In the shape of the curve lies much chemistry and an interesting summary of what we have learned so far about acids and bases. The titration of a strong acid with a strong base produces the following titration curve:

Note the sharp transition region near the equivalence point on the above figure. Also remember that the equivalence point for a strong acid-strong base titration curve is exactly 7 because the salt produced does not undergo any hydrolysis reactions. However, if a strong base is used to titrate a weak acid, the pH at the equivalence point will not be 7. There is a lag in reaching the equivalence point, as some of the weak acid is converted to its conjugate base. You should recognize the pair of a weak acid and its conjugate base as a buffer. In the following diagram, we see the resultant lag that precedes the equivalence point, called the buffering region. In the buffering region, it takes a large amount of NaOH to produce a small change in the pH of the receiving solution.

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Because the conjugate base is basic, the pH will be greater than 7 at the equivalence point. You will need to calculate the pH using the Henderson-Hasselbalch equation, and inputting the pK b and concentration of the conjugate base of the weak acid. The titration of a base with an acid produces a flipped-over version of the titration curve of an acid with a base. pH is decreased upon addition of the acid. Note that the pH of a solution at the equivalence point has nothing to do with the volume of titrant necessary to reach the equivalence point; it is a property inherent to the composition of the solution. The pH at the equivalence point is calculated in the same manner used to calculate the pH of weak base solutions in Calculating pHs. When polyprotic acids are titrated with strong bases, there are multiple equivalence points. The titration curve of a polyprotic acid shows an equivalence point for the each protonation:

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The titration curve shown above is for a diprotic acid such as H2SO4 and is not unlike two stacked titration curves for a strong base titrating a weak acid. For a diprotic acid, there are two buffering regions and two equivalence points. This proves the earlier assertion that polyprotic acids lose their protons in a stepwise manner.
More Titration Curves Examples:

titration curve of a monoprotic acid

titration curve of a diprotic acid

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titration curve with indicators

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titration curve of a base

titration curve of a buffered system

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titration curve of a buffered system

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Sample Titration Problem: You have been asked to determine the exact concentration of a sulfuric acid solution. You titrate 4.00 mL of the solution to a phenolphthalein end point. The titration takes 23.42 mL of 0.1037 M NaOH. What is the molarity of the sulfuric acid solution? Method: 1. 2. 3. 4. Write a balanced equation. Calculate the moles of base used. Calculate the moles of acid reacted. Calculate the molarity of the acid.

Step 1: H2SO4 + 2 NaOH -----> Na2SO4 + 2 H2O Step 2: The moles of NaOH can be obtained from the volume/concentration information:

23.42 mL 1 L 1000 ml
Step 3:

0.1037 mol 1L

= 2.4286 x 10-3 mol NaOH

Here's where the balanced equation is important. More students do titration calculations incorrectly because they skip this step than for any other reason! The mole ratios are vital. You might want to consider writing out this step even for reactions, such as KHP with NaOH, where the mole ratios are 1:1. It will help to make sure you remember to do this step when the ratios aren't 1:1.

2.4286 x 10-3 mol NaOH

Step 4:

1 mol H2SO4 2 mol NaOH

= 1.2143 x 10-3 mol H2SO4

All of the moles of sulfuric acid titrated in the reaction came from one place: the original sample of sulfuric acid that you measured. Since you know the volume of that sample (4.00 mL) and the number of moles in the sample (see Step 3), calculating the molarity of the sulfuric acid is easy:

1.2143 x 10-3 mol H2SO4 4.00 ml

1000 ml 1L

= 0.303 M H2SO4

All titration calculations are similar to this. There is one titration that has little different approach. When a standardization is done on a solution like sodium hydroxide, a solid acid that can be dried will be used. A calculation 23

involving a solid, like KHP, potassium hydrogen phthalate, just means that you calculate the moles of KHP from the molar mass instead of from a molarity and a volume. Is titration is important as you cannot sufficiently dry NaOH solid to get an accurate solution of NaOH. So, you make the solution at the concentration you need, as best you can. Then check it against an acid that can be dried, like KHP. It is sort of a round about way to determine the concentration of the base, but it is how a chemist does it. Another Example: Evaluate [H+] and pH in the titration of 10.0 mL 1.0 M HCl solution with 1.0 M NaOH solution, and plot the titration curve. Solution: The amount of moles of acid present = Volume of acid x Concentration of the acid mola = MaVa mola =
10.0ml 1.0mol 1liter = .0010mol 1 1liter 1000ml

The amount of moles of base added = Volume of base x Concentration of the base molb = MbVb The amount of moles of acid left = mola - molb = MaVa - MbVb The concentration of acid and thus [H+]
M a V a M b Vb V a + Vb

The terms Va + Vb need to be included as there is a dilution of the acid and base as the total volume is increased With the above formula, we can built a table for various values as shown.

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Rules for Naming Acids

1. If the anion does not contain oxygen, the acid is named with the prefix hydro- and the suffix ic attached to the anion. Example

HCl hydrochloric acid chlorine HBr hydrobromic acid bromine

because the anion is because the anion is

2. When the anion contains oxygen, the acid name is formed from the non-oxygen element in the anion with the suffix ic or ous. -ate becomes -ic -ite becomes -ous Example H2SO4 sulfuric acid because sulfate is the anion ate becomes -ic H3PO4 phosphoric acid because phosphate is the anion ate becomes ic H2SO3 sulfurous acid because sulfite is the anion -ite becomes ous

Naming Acids Flow Chart

Does the anion contain oxygen? no yes

hydro + element name + ic -ite

Check the ending of the anion -ate

element name + -ous

element name + -ic

End all names with the word acid

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