Experiment 7: Acyl Compounds: Soap and Detergent Results and Discussion A.

Solubility and acidity of carboxylic acids The carboxylic acid is considered to be a highly polar organic functional group. This polarity results from the presence of a strongly polarized carbonyl (C=O) group and hydroxyl (O-H) group. Oxygen is a relatively electronegative atom and when covalently bound to carbon and particularly hydrogen, a strong permanent dipole is created. In the case of carboxylic acids, the O-H group is even more strongly polarized than the O-H group of alcohols due to the presence of the adjacent carbonyl group. Carboxylic acids have a greater number of dipoles and stronger dipoles than other organic compounds, and thus can form more and stronger Hbonds with other substances capable of H-bonding interactions. Also, as a result of the ability to form "solubilizing" H-bonding interactions with water and other polar, protic solvents, carboxylic acids display relatively high water solubilities compared to comparable organic compounds. In the experiment, the solubilities of acetic acid, benzoic acid and sodium benzoate were compared. Both the benzoate and acetic acid dissolved in water while the benzoic were not fully dissolved. This can be explained by the polarity of the former and the non polarity of the benzoic acid. Also, carboxylic acids are acidic in nature. The term "acid" is reserved for those compounds that transfer protons measurably to water. The mineral acids (HCl, HBr, HI, H2SO4, H3PO4) are defined as "strong acids" because they undergo complete dissociation, donating a proton to water to form the hydronium ion. On the other hand, simple hydrocarbons (alkanes, alkenes, alkynes, aromatics) and even many polar organic compounds such as alcohols, esters, amides, aldehydes and ketones, generally are considered to be "nonacidic" because they do not dissociate in water. These compounds may ionize in the presence of sufficiently strong bases, but they do not ionize appreciably in water. Carboxylic acids are referred to as "weak acids" because they partially dissociate in water.

The ability of carboxylic acids to ionize and behave as acids is a direct function of the electronic properties and bonding order of the atoms that make up the carboxyl (COOH) group. This functional group consists of a carbonyl group that has an electron deficient carbon atom due to pi bonding (double bond) to electronegative oxygen. This carbonyl carbon also is directly linked to, and in conjugation with, a second electronegative oxygen atom bearing a hydrogen atom. This electronic arrangement allows for loss of a proton and ionization because electron density is "pulled" from the hydroxyl hydrogen through the conjugated carboxyl group, and the charge formed upon ionization (in the conjugate base) is stabilized by resonance delocalization. The stabilization of the conjugate base (carboxylate) by resonance is probably best represented by the "composite" resonance structure.

Largely due to this stabilization, acids are "somewhat acidic" with pKas typically ranging from 3 to 5. Basing on the observation above, there a few undissolved particles in the solution of phenol and NaOH. This means that phenol is a weaker acid than benzoic acid. Alcohols such as phenols are similar to carboxylic acids in that they contain an OH group. In alcohols ionization of the OH group yields an alkoxide (anion) as the conjugate base where the oxygen alone bears the negative charge because resonance delocalization is not possible; the carbon adjacent to the alkoxide oxygen is sp3 hybridized. Since the charge in alkoxide base is not stabilized to the same degree as the conjugate base formed from carboxylic acids (where the charge is delocalized by resonance), it is less likely to form. Thus alcohols are less acidic than carboxylic acids.

Phenols are weak acids since the phenyl ring linked to an alcohol functionality exerts a electron withdrawing effect further polarizing this function group, and conjugate base formation is promoted by aromatic ring associated resonance stabilization of the resultant anion. However, phenols are generally less acidic than carboxylic acids based on the electronic nature of atoms over which the charge of the conjugate base is delocalized. In the case of carboxylic acids, the resultant charge is delocalized over two electronegative oxygen atoms. In the case of phenols the charge of the conjugate base is delocalized over only one electronegative oxygen atom. Also. when NaHCO3 was used, benzoic acid dissolved but the phenol did not. This is because phenol is not acidic enough to neutralize NaHCO3 to give carbonic acid (CO2 + H2O). Thus, we can deduce that it is not much soluble in this reagent compared to that in NaOH, as seen from the resulting oily layer formation at the bottom part of the test tube which indicates only slight miscibility. Hydrolysis is a reaction with water resulting to breaking down of complex molecules. After adding water to acetyl chloride there was a strong vinegar odor. CH3CH2- COCl + H2O CH3CH2-COOH + HCl The hydrochloric acid produced affirmed the test with the litmus paper wherein the blue litmus paper turned red. Acetic anhydride hydrolyzes to give acetic acid which was observed as a faint vinegar odor. This explains the turning of the blue litmus paper to red. (CH3CH2)2-O + H2O 2 CH3CH2-COOH Also, both acyl chloride and acetic anhydride evolved heat before they were heated. Benzamide hydrolyzes to form carboxylic acids. However, heat is necessary to dissolve it in water. In the litmus test, the blue litmus paper turned red indicating the formation of the carboxylic acid.

C6H5- CON + H2O C6H5 COOH Saponification Fats and oils can be broken down into their component parts by alkaline hydrolysis of the three ester linkages yielding chain carboxylate salts and glycerol. The sodium salts of fatty acids are called soap. The alkaline hydrolysis of fats and oils is commonly called saponification. A synthetic detergent, a sodium alkyl sulfate called sodium dodecylsulfate, can be prepared by reacting dodecyl alcohol (dodecanol) with sulfuric acid.

The resulting dodecylsulfate is converted to the sodium salt by a reaction with sodium hydroxide.

In the test for the soap and detergents pH, blue litmus paper remained unchanged while the red litmus paper turned to blue, supporting that both compounds are basic. Soaps and detergents are similar in their general structure and properties, but different in their composition and some specific properties such as emulsifying properties, behavior in hard water and ability to react with mineral acids. As a result of their molecular structures, soaps and detergents are both capable of emulsifying or dispersing oils and similar water-insoluble substances. This ability comes from the molecular structure of soaps and detergents. When a soap or detergent is added to water that contains oil or other water-insoluble materials, the soap or detergent molecules surround the oil droplets. The oil or grease is dissolved in the alkyl groups of the soap molecules while the ionic end allows the micelle to dissolve in water. As a result, the oil droplets are emulsified or dispersed throughout the water and can be rinsed away. The sodium and potassium salts of most carboxylic acids are water soluble. However, the calcium, magnesium, and iron salts are not. Thus, when soaps are placed in hard water that contains such ions, an insoluble, curdy solid forms. This was observed the experiment when the addition of hard water produced cottony white precipitate. The precipitates can be seen in the soapy water and are referred to as soap scum. This soap scum can form deposits on clothes causing them to be gray or yellow in color.

The calcium, magnesium, and iron forms of most detergents are more soluble in water than the corresponding soap compounds. Consequently, detergents function almost as well in hard water as they do in soft water. It does not form precipitates with metal ions, reducing the discoloration of clothes due to the precipitated soap. Soaps, the sodium salts of fatty acids, are water soluble, but the fatty acids themselves are not. With the addition of acid, the soap produced small amounts of precipitate. This is because as salts of weak acids, they are converted by mineral acids into free fatty acids.

These fatty acids are less soluble than the sodium or potassium salts and form a precipitate or soap scum. Because of this, soaps are ineffective in acidic water. Acidification of detergents, on the other hand, produces acids which are often water soluble and was evidenced by the clear solution after the addition of acid.