Alcohols Although you may be familiar with "alcohol as a beverage, the word actually represents an entire classification of organic

molecules and not just one substance. Alcohols contain the OH (hydroxyl) functional group attached to a saturated carbon. Notice that we did not call this the hydroxide ion, because this group does not act as an ionic substance. Alcohols are classified into three categories: primary (1), secondary (2) and tertiary (3). This classification is based on the number of carbon-containing groups (R for an alkyl or an aromatic group) attached to the carbon bearing the hydroxyl group. If the carbon bearing the OH has one R group, the molecule is a primary alcohol. If two R groups are attached, it is a secondary alcohol. If three Rgroups are attached, the alcohol is tertiary.
CH3 CH3 CH3 CH3 CH2 OH CH3 CH OH CH3 C OH

ethanol (primary)

2-propanol (secondary)

2-methyl-2-propanol (tertiary)

I. Physical Properties of Alcohols The hydroxyl group present in all alcohols is a polar functional group. The polarity of this group allows alcohols to form hydrogen bonds. Small chain alcohols are able to mix with water because of the hydrogen bonding interactions that will occur between the hydroxyl functional group and the water. If the R-group of the alcohol becomes too large however, the solubility of the alcohol will decrease. II. Chemical Properties of Alcohols The classification of an alcohol as primary, secondary or tertiary (see above) affects the chemical properties of the alcohols. This difference in chemical properties can be used as a means of identification. The Lucas test and the chromic acid test are two common methods used to distinguish among primary, secondary and tertiary alcohols. A. Lucas Test The Lucas reagent contains zinc chloride and hydrochloric acid. When the Lucas reagent is allowed to react with an alcohol, an alkyl halide is formed. This alkyl halide will not be soluble in water, thus cloudiness or a second layer of droplets will form if the test is positive. With this reagent, tertiary alcohols react immediately, secondary alcohols in 3 to 10 minutes, and primary alcohols may take an hour or longer, or may never react.

Phenols Phenols are closely related to alcohols because of the presence of the hydroxyl ( OH) group. In phenols, however, the hydroxyl group is directly bonded to an aromatic group, such as benzene. Phenol compounds often have curious but useful properties. Some are found in preservatives or medications. The chemistry of phenols is different than that of alcohols. Concentrated solutions of the compound phenol are quite toxic and can cause severe burns. In this experiment, we are using an aqueous solution of phenol. IV. Chemical Properties of Phenols Phenols react differently than alcohols. This is why they are given their own functional group and are not technically alcohols. B. Ferric Chloride test Addition of aqueous ferric chloride to a phenol creates a colored solution. Depending upon the structure of the phenol, the color can vary from green to purple. * Properties of Alcohols and Phenols * * Introduction * As has been mentioned before, over 20 million organic compounds have been identified. If each substance had to be studied as an entity completely separate from all the other substances, the study of organic chemistry as a whole would be impossible; that is to say, even more impossible than you currently believe it to be. Fortunately, the subject can be organized and it is often organized around the concept of the functional group. A functional group is an atom or group of atoms, bonded together in a certain way, that, as part of a molecule, will impart certain physical and chemical characteristics to the molecule as a whole. It is the case that the rest of the molecule can modify the characteristics of the functional group. It is also the case that if the rest of the molecule is an alkyl group the modifications may be modest. On the other hand, other functional groups in the molecule, especially if they are close by, are more likely to profoundly modify the characteristics of the functional group in question. The functional group we are considering in this experiment is the hydroxy (or hydroxyl) functional group, -OH. This group shows up in a number of guises in organic compounds. The functional groups we will consider in this experiment are alcohols and phenols. In alcohols the -OH group is attached to a tetrahedral carbon atom. If the carbon atom is bonded to three hydrogens in addition to the -OH, the alcohol is methanol. If the carbon that is bonded to the -OH is bonded to one carbon and two hydrogens, the alcohol is a primary (1o) alcohol. If the carbon that is bonded to the -OH is bonded to two carbons and one hydrogen, the alcohol is a secondary (2o) alcohol. If the carbon that is bonded to the -OH is bonded to three carbons, the alcohol is a tertiary (3o) alcohol. All of these alcohols share some characteristics but other characteristics are different owing to their different structures. In phenols the -OH group is directly attached to a carbon that is part of an aromatic ring. Alcohols and phenols are similar in some ways, but there are enough

differences so that they are considered different functional groups. One major difference is that phenols are typically about a million times more acidic than alcohols. Addition of sufficient aqueous sodium hydroxide to a phenol will cause the -OH group of most of the molecules present to be deprotonated; this will not happen to an alcohol. * Physical Properties * The larger an alcohol or phenol the higher the boiling point, usually. As the alcohol size increases the probability that the alcohol will be a solid increases. Many phenols are solids. Small alcohols are water soluble because the hydroxyl group can hydrogen bond with water molecules. But as the size of the alkyl group increases the solubility in water decreases. This is the result of the alkyl group disrupting hydrogen bonding among the water molecules. If the disruption becomes large enough the water molecules, in effect, expel the alcohol molecules to reestablish hydrogen bonding. A cartoon showing this is seen above. The situation is similar for phenols. If nonpolar groups (like alkyl groups) are attached to the aromatic ring the water solubility of the phenol decreases. [This is why nonpolar groups are sometimes called hydrophobic.] * Chemical Properties * We shall focus on chemical reactions that can help to distinguish alcohols from phenols and to distinguish among the classes of alcohols. 1. Lucas Test This test is used to distinguish among primary, secondary, and tertiary water soluble alcohols. Lucas reagent is a mixture of concentrated hydrochloric acid and zinc chloride. Zinc chloride is a Lewis acid, which when added to hydrochloric acid makes it even more acidic. Water soluble tertiary alcohols react with Lucas reagent almost immediately to form an alkyl chloride which is insoluble in the aqueous solution. The formation of a second liquid phase in the test tube almost as soon as the alcohol initially dissolves is indicative of a tertiary alcohol. A secondary alcohol reacts slowly to form a chloride and, after heating a little, gives a second phase, usually within 10 minutes. Primary alcohols and methanol do not react under these conditions. In the case of tertiary alcohols the chloride is usually attached to the carbon that held the hydroxyl group. In the case of secondary alcohols, it is often the case that the chlorine is attached to the carbon that held the hydroxyl, but rearrangements are possible. * Another Introduction * The general formula of an alcohol is ROH in which the R is an aliphatic hydrocarbon group. Alcohols may be looked upon as derivatives of water, HOH. One hydrogen of water is substituted by an alkyl group, R. Like water, alcohols show hydrogen bonding. As the chain of the R group increases the hydrocarbon character of the compound overshadows the polar character of the OH group. Consequently, the solubility and boiling point of an alcohol are affected by the length of the carbon chain and the shape of the molecule. The short chain alcohols are soluble in water, whereas the longer chain alcohols are insoluble in water. In general a molecule which is more compact (i.e., more branched) will be more soluble in water and will have a lower boiling point than the straight chain isomer. Phenols are aromatic alcohols, in which R is an aromatic ring. This experiment will demonstrate some of the properties of alcohols and phenols. Although alkyl alcohols have an -OH group, they do not ionize in water, whereas phenols ionize like acids

(donating a proton to water). The -OH group of alkyl alcohols can be positioned on different carbon atoms of the carbon chain and are classified as primary (1), secondary (2), or tertiary (3) alcohols depending on whether the -OH group is attached to a carbon with 1, 2 or 3 other carbon atoms attached to it. These different alcohols react differently with Lucas reagent and with Bordwell-Wellman reagent; hence these reagents can be used for identifying the class of alcohol. The relative acidity of phenols can be used to characterize this class of alcohols relative to the alkyl alcohols. This property will be exploited in the identification of phenol. _____________________________________________________________________________ Tollens' reagent is a chemical reagent most commonly used to determine whether a known carbonyl-containing compound is an aldehyde or aketone. It is usually ammoniacal silver nitrate, but can also be other mixtures, as long as aqueousdiamminesilver(I) complex is present. It was named after its discoverer, Bernhard Tollens. A positive test with Tollens' reagent results in elemental silver precipitating out of solution, occasionally onto the inner surface of the reaction vessel, producing a characteristic and memorable "silver mirror" on the inner vessel surface. _____________________________________________________________________________