Esther Faith S.

Gabriel BS-PH 1-A ACIDS & BASES

A. Concepts on Acids and Bases 1. Arrhenius Theory of Acid-Base Behavior The first quantitative approach to acid-base equilibria was developed around 1884 by the Swedish chemist Svante Arrhenius. According to his Arrhenius theory, an acid is any compound or ion which yields hydrogen ions in water solution and a base is any compound or ion which yields hydroxyl ions in water solution. The approach taken by Arrhenius with acids and bases was in accordance with his general approach to substances in aqueous solution. Materials which dissolved in whole or in part as ions were, and still are, called electrolytes. A strong electrolyte, like sodium chloride, was a substance which dissociated completely into ions while a weak electrolyte remained partially in molecular form. Thus a strong acid is a strong electrolyte which ionized completely to give hydrogen ions in aqueous solution. All of the common strong acids sulfuric acid, H2SO4; nitric acid, HNO3; hydrochloric acid, HCl; and perchloric acid, HClO4 easily fit in this category. Likewise, a strong base is a strong electrolyte which ionized completely to give hydroxyl ions in aqueous solution. The common strong bases, NaOH and KOH, fit in this category. Acid-base reactions are then simply the reaction of the hydrogen ion with the hydroxyl ion as a neutralization reaction, H+(aq) + OH-(aq) --> H2O. The remaining ions simply continue to exist as a solution of a salt. The reaction including these "bystander ions" could be written as H+(aq) + Cl-(aq) + Na+(aq) + OH-(aq) --> Na+(aq) + Cl-(aq) + H2O The Arrhenius concept was not intended to, and does not, deal with acid-base chemistry in solvents other than water. Even in water, however, it has deficiencies. Ammonia, NH3, clearly behaves in a qualitative manner as a base and reacts to neutralize acids. However, ammonia does not contain a hydroxide ion. This is of itself no obstacle because ammonia might well produce hydroxyl ion by reaction with water: NH3(aq) + H2O --> NH3.HOH --> NH4OH --> NH4+(aq) + OH-(aq) However, no experimental evidence for the existence of NH4OH has yet been foumd. For these two reasons, the Arrhenius concept is no longer considered an adequate treatment of acids and bases even in aqueous solution. 2. Bronsted-Lowry Theory of Acid-Base Behavior The Arrhenius theory was the only theory used to explain the behaviour of acids and bases for about forty years. In 1923, J. N. Bronsted in Denmark and T. M. Lowry in England independently, and almost simultaneously, proposed the modern "protonic" or BronstedLowry theory of acid-base behaviour. According to the Bronsted-Lowry concept, an acid is

any compound or ion which can give up a proton, while a base is any compound or ion which can accept a proton. Any species which can either accept or give up a proton is said to be amphiprotic. Thus the water molecule is amphiprotic, since it can give up a proton, H2O --> H+ + OH-, to form the hydroxyl ion OH-. Alternatively, water can accept a proton to form the hydronium ion H3O+, according to the equation H+ + H2O --> H3O+. The above two equations can be combined to give the dissociation equation for water: 2H2O --> H3O+ + OH-. The Bronsted-Lowry concept is an extension of the Arrhenius concept in that all Arrhenius bases, being sources of hydroxide, can accept protons. Ammonia and amines will also accept protons to form the corresponding ammonium ions, so the existence of NH4OH is no longer necessary to explain the action of ammonia as a base. The Bronsted-Lowry concept also is useful in protonic solvents other than water, such as liquid ammonia or glacial acetic acid, where the Arrhenius concept is not useful. We will, however, generally confine our discussion to aqueous solutions because they are so much more important. 3. Lewis Explanation of Acid-Base Behavior The basic principles of the Lewis theory of acid-base behaviour were also set down in 1923, by the American physical chemist G. N. Lewis. The Lewis definitions of acids and bases are even more inclusive than the Bronsted definitions. The Lewis definitions are that an acid is an electron-pair acceptor and a base is an electron-pair donor. Since a base like ammonia, H3N:, has a lone pair of electrons, it can be considered to "donate" them to a proton in forming the conjugate acid NH 4+. The Lewis definitions are used to explain the effect of compounds such as AlCl3, which acts as an acid in nonaqueous organic solvents, on organic reactions. In protonic solvents, however, the Lewis definitions are far less useful than are the Bronsted definitions. Properties of acids and bases Properties of acids include the following:

React with most metals to form hydrogen gas Taste sour (like lemons) Frequently feel "sticky" Usually gases or liquids Acids turn blue litmus to red Acids corrode active metals Acids neutralize bases in a neutralization reaction.

Properties of bases include: Feel "slippery". (FYI: The slippery feeling is caused because your skin dissolves a little when you touch them.) Taste bitter (like baking soda) React with oils and greases (that's why they're used as drain and window cleaners) Frequently solids (though ammonia is a gas that's usually dissolved in water)

Bases turn red litmus to blue. Bases release a hydroxide ion into water solution. STRONG ACIDS AND STRONG BASES

The common acids that are almost one hundred percent ionized are: HNO3 - nitric acid HCl1 - hydrochloric acid H2SO4 - sulfuric acid HClO4 - perchloric acid HBr1 - hydrobromic acid HI1 - hydroiodic acid The acids on this short list are called strong acids, because the amount of acid quality of a solution depends upon the concentration of ionized hydrogens. You are not likely to see much HBr or HI in the lab because they are expensive. You are not likely to see perchloric acid in a school setting because it can explode if not treated carefully. Other acids are incompletely ionized, existing mostly as the unionized form. Incompletely ionized acids are called weak acids, because there is a smaller concentration of ionized hydrogens available in the solution. Do not confuse this terminology with the concentration of acids. The differences in concentration of the entire acid will be termed dilute or concentrated. Muriatic acid is the name given to an industrial grade of hydrochloric acid that is often used in the finishing of concrete. In the list of strong acids, sulfuric acid is the only one that is diprotic, because it has two ionizable hydrogens per formula (or two mols of ionizable hydrogen per mol of acid). (Sulfuric acid ionizes in two steps. The first time a hydrogen ion splits off of the sulfuric acid, it acts like a strong acid. The second time a hydrogen splits away from the sulfate ion, it acts like a weak acid.) The other acids in the list are monoprotic, having only one ionizable proton per formula. Phosphoric acid, H3PO4, is a weak acid. Phosphoric acid has three hydrogen ions available to ionize and lose as a proton, and so phosphoric acid is triprotic. We call any acid with two or more ionizable hydrogens polyprotic. Likewise, there is a short list of strong bases, ones that completely ionize into hydroxide ions and a conjugate acid. All of the bases of Group I and Group II metals except for beryllium are strong bases. Lithium, rubidium and cesium hydroxides are not often used in the lab because they are expensive. The bases of Group II metals, magnesium, calcium, barium, and strontium are strong, but all of these bases have somewhat limited solubility. Barium hydroxide has a high enough solubility to really call it the only dibasic strong base. Magnesium hydroxide has a particularly small solubility. Potassium and sodium hydroxides both have the common name of lye. Soda lye (NaOH) and potash lye (KOH) are common names to distinguish the two compounds. LiOH1 - lithium hydroxide NaOH1 - sodium hydroxide KOH1 - potassium hydroxide RbOH1 - rubidium hydroxide

CsOH1 - cesium hydroxide (Mg(OH)2 - magnesium hydroxide) (Ca(OH)2 - calcium hydroxide) (Sr(OH)2 - strontium hydroxide) Ba(OH)2 - barium hydroxide The bases of Group I metals are all monobasic. The bases of Group II metals are all dibasic. Aluminum hydroxide, Al(OH)3 is tribasic. Any material with two or more ionizable hydroxyl groups would be called polybasic. Most of the alkaline organic compounds (and some inorganic materials) have an amino group -(NH2) rather than an ionizable hydroxyl group. The amino group attracts a proton (hydrogen ion) to become -(NH3 )+. (The dash before the (NH3)+ or (NH2) indicates a single bonding electron, so this is attached to something else by a covalent bond.) By the Lowry- Brnsted definition, an amino group definitely acts as a base, and the effect of removing hydrogen ions from water molecules is the same as adding hydroxide ions to the solution. Titrations Titrations are not all that hard to understand. In fact, the word "titration" comes from the Greek titros which means "to figure out the molarity of an acid or base solution" and the Latin ations which means "by neutralizing it with a solution whose concentration you already know". That's what a titration is. Let's say you have an acidic solution and wanted to figure out the molarity. Well, you can't do that directly, because you can't count acid molecules. They're too small. You can, however, make a basic solution with a concentration that you already know. If you keep adding base to the acid, eventually all of the acid molecules will be neutralized and the solution will turn from an acid to a base. If you know how many base molecules you added to the solution before the solution gets neutralized (and you will, because you'll add the solution drop-by-drop), you can figure out how much acid was in the solution in the first place. Of course, this leads to an interesting problem: How can you tell when the solution gets neutralized? The answer: Indicators! Indicators are chemical compounds that turn different colors when they're in solutions with different pH's. The indicators you'd most likely work with turn color when the solution becomes neutralized. Litmus, for example, is red in acid solutions and blue in basic solutions. Phenolphthalein (pronounced fee-no-thayleen) is clear in acid solutions and pink in basic solutions. M1V1 = M2V2 M1 stands for the molarity of the acid V1 stands for the volume of the acid you use M2 stands for the molarity of the base V2 stands for the volume of the base you use

Example: If it takes 55 mL of 0.1 M NaOH solution to neutralize 450 mL of a HCl solution of unknown concentration, what's the molarity of the acid?

Solution: Before you can do anything, you need to translate this into something that makes sense. Let's go through it slowly.

M1, in our equation, stands for the molarity of the acid. Since that's what we're trying to find, we'll call that X. V1 stands for the volume of the acid we use. Since HCl is an acid, the volume of acid is 450 mL M2 stands for the molarity of the base. Since NaOH is a base, the molarity was stated in the problem to be 0.1 M V2 stands for the volume of the base. The problem says that we used 55 mL of base, so that's M2.

Now, all we need to do is plug it into the equation: (X)(450 mL) = (0.1 M)(55 mL) X = 0.12 M