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2.14: Organic Functional Groups: H-bond donors

  • Page ID
    182848
  • Learning Objective

    • distinguish between organic compounds that are H-bond donors versus H-bond acceptors

    H-bond donors vs H-bond acceptors

    Compounds with H-bonding as their dominant intermolecular force (IMF) are BOTH H-bond donors and H-bond acceptors. They are H-bond donors because they have a highly polar hydrogen atom bonded to a strongly electronegative atom, primarily nitrogen, oxygen, or fluorine (NOF). Because there is an equivalent partial negative charge on the atom bonded to hydrogen (mostly NOF), this atom can accept H-bonds from another atoms. Since H-bond donors are ALWAYS H-bond acceptors, we simplify communication to "H-bond donor". There are two H-bonding interactions for H-bond donors. The strongly electronegative elements (primarily nitrogen, oxygen, and fluorine) will always form a relatively large partial negative charge when bonded with carbon. These elements can accept H-bonds when they are part of the organic molecule. In this situation, there is only one H-bonding interaction. The diagram below illustrates the similarities and differences between H-bond donors and H-bond acceptors. Water and alcohols may serve as both donors and acceptors, whereas ethers, aldehydes, ketones and esters can function only as acceptors. Similarly, primary and secondary amines are both donors and acceptors, but tertiary amines function only as acceptors.

    hbonds1.gif

    Exercise

    1. Classify the compounds below as H-bond donors, H-bond acceptors, or neither.

    Hbond donors acceptors.png

    Answer

    1.

    Hbond donors acceptors answer.png

    Comparing Physical Properties of H-bond Donors vs H-bond Acceptors

    Once we are able to recognize compounds that can exhibit intermolecular hydrogen bonding, the relatively high boiling points they exhibit become understandable. The data in the following table serve to illustrate this point.

    Compound Formula Mol. Wt. Boiling Point Melting Point
    dimethyl ether CH3OCH3 46 –24ºC –138ºC
    ethanol CH3CH2OH 46 78ºC –130ºC
    propanol CH3(CH2)2OH 60 98ºC –127ºC
    diethyl ether (CH3CH2)2O 74 34ºC –116ºC
    propyl amine CH3(CH2)2NH2 59 48ºC –83ºC
    methylaminoethane CH3CH2NHCH3 59 37ºC
    trimethylamine (CH3)3N 59 3ºC –117ºC
    ethylene glycol HOCH2CH2OH 62 197ºC –13ºC
    acetic acid CH3CO2H 60 118ºC 17ºC
    ethylene diamine H2NCH2CH2NH2 60 118ºC 8.5ºC

    Alcohols boil cosiderably higher than comparably sized ethers (first two entries), and isomeric 1º, 2º & 3º-amines, respectively, show decreasing boiling points, with the two hydrogen bonding isomers being substantially higher boiling than the 3º-amine (entries 5 to 7). Also, O–H---O hydrogen bonds are clearly stronger than N–H---N hydrogen bonds, as we see by comparing propanol with the amines.

    acohdimr.gif

    As expected, the presence of two hydrogen bonding functions in a compound raises the boiling point even further. Acetic acid (the ninth entry) is an interesting case. A dimeric species, shown on the right, held together by two hydrogen bonds is a major component of the liquid state. If this is an accurate representation of the composition of this compound then we would expect its boiling point to be equivalent to that of a C4H8O4 compound (formula weight = 120). A suitable approximation of such a compound is found in tetramethoxymethane, (CH3O)4C, which is actually a bit larger (formula weight = 136) and has a boiling point of 114ºC. Thus, the dimeric hydrogen bonded structure appears to be a good representation of acetic acid in the condensed state.

    A related principle is worth noting at this point. Although the hydrogen bond is relatively weak (ca. 4 to 5 kcal per mole), when several such bonds exist the resulting structure can be quite robust. The hydrogen bonds between cellulose fibers confer great strength to wood and related materials. For additional information on this subject Click Here.