Hydrogen Bonding : from wikidavis and other sites with Chem 14c student commentary

In red or italics

Donors and Acceptors

In order for a hydrogen bond to occur there must be both a hydrogen donor and an acceptor present. The donor in a hydrogen bond is the atom to which the hydrogen atom participating in the hydrogen bond is covalently bonded, and is usually a strongly electronegative atom such as N,O, or F(rarely anything else) . The hydrogen acceptor is the neighboring electronegative ion or molecule, and must posses a lone electron pair in order to form a hydrogen bond.

Why does a hydrogen bond occur? Since the hydrogen donor is strongly electronegative, it pulls the covalently bonded electron pair closer to its nucleus, and away from the hydrogen atom. The hydrogen atom is then left with a partial positive charge, creating a dipole-dipole attraction between the hydrogen atom bonded to the donor, and the lone electron pair on the acceptor. ( also note that this doesn't have to be a dipole dipole interaction as noted on page 205 of the thinkbook, in this case F- is an ion and the CH3CH2OH molecules are dipoles so we have an ion dipole interaction ) This results in a hydrogen bond.

Types of hydrogen bonds

Hydrogen bonds can occur within one single molecule, between two like molecules, or between two unlike molecules. Intramolecular hydrogen bonds Intramolecular hydrogen bonds are those which occur within one single molecule. This occurs when two functional groups of a molecule can form hydrogen bonds with each other. In order for this to happen, both a hydrogen donor an acceptor must be present within one molecule, and they must be within close proximity of each other in the molecule. For example, intramolecular hydrogen bonding occurs in ethylene glycol (C2H4(OH)2) between its two hydroxyl groups due to the molecular geometry.

Intermolecular hydrogen bonds Intermolecular hydrogen bonds occur between separate molecules in a substance. They can occur between any number of like or unlike molecules as long as hydrogen donors and acceptors are present an in positions in which they can interact.For

example, intermolecular hydrogen bonds can occur between NH3 molecules alone, between H2O molecules alone, or between NH3 and H2O molecules.

http://chemwiki.ucdavis.edu/Physical_Chemistry/Quantum_Mec hanics/Intermolecular_Forces/Hydrogen_Bonding

http://www.bio.brandeis.edu/classes/biochem104/hydrogen_bonds.pdf This quoted from link above: , Quantum mechanical calculations show that the free electron pairs found on nitrogen and oxygen are delocalized around the hydrogen nucleus similar to the way electrons are shared by bonded atoms in a normal covalent bond.

What does this mean in relation to why do we require a lone pair of electrons. If we view hydrogen attached to the donor atom (N, O, F) as a H very deficient of electrons we can get an idea of why we need an electron pair on the acceptor atom. View the hydrogen bonding between the H delta + and the acceptor with the electrons delta as a bond that has "covalent character" (before I confuse you, read the link above page 2 this clarifies it is still an electrostatic interaction, it is NOT a covalent bond but it is a good way to understand the need for an electron pair ) . Seeing it this way while remembering this is still a electrostatic attractive force and is hydrogen NOT covalent bonding , the lone pair is "completing" the electron deficient hydrogen through the hydrogen bonding between the donor and acceptor . Also this electron pair is needed to form the hydrogen bond without it be simply have a dipole-dipole interaction if we could some how have a polar molecule with no lone pairs and stick the delta area of the molecule it right next too the hydrogen attached to the hydrogen bond

donor in water with the H delta + next to the delta - of this other molecule, we could have a dipole dipole interaction but no hydrogen bonding. BUT! if we have water, the 2 lone pairs not participating in the covalent bond can participate as hydrogen bond acceptors,

note : also if you are interested in NMR and hydrogen bonding and the idea of covalent character go here :http://www.ias.ac.in/currsci/nov25/articles8.htm I thought it was quite interesting

Question Practice Problem 2 Propionic acid vs methyl acetate

Methyl Acetate

propionic acid

It isn't about the number of hydrogens but the order in which they are bonded therefore it is about how the molecule is arranged strucurally not the molecular formula. For hydrogen bonding to occur we need a hydrogen bond donor, a H atom attached to N, O, or F (high EN atom) and we need a hydrogen acceptor, in this case the O in the molecule of propionic acid is also an acceptor as well as the double bonded O from the carboxylic acid portion of this molecule. In this case propionic acid has a H directly attached to an O, This O---H bond on propionic acid serves as a hydrogen bond donor. The H has a delta + charge and is attached to a O , this bond allows the H form a electrostatic attraction, or participating in hydrogen bonding with another atom in a neighboring atom in which there is a lone pair and this atom should have a high electrom density in order to attract the delta + .

What can be a acceptor then!? Well we have to first consider that hydrogen bonding is paired with other intermolecular forces. Hydrogen bonding can and often occurs with another intermolecular force. Often it occurs in areas where we would usually expect another interaction such as dipole dipole interactions or ion dipole interaction. Hydrogen bonding then occurs with these intermolecular forces if and when we have the hydrogen bond donor and a proper acceptor. Whats the acceptor then? First, Requirements for the job of acceptor: It has a high electron density, it must have a lone pair which can participate in the hydrogen bond and act as an acceptor of the delta + charge of the H. But now determining where these atoms that are acceptors occur and dont: We cant limit the acceptor atom by its position in or not within a molecule. The acceptor there fore can various atoms with a large electron density, these atoms could be ions such as F- , atoms within a molecule with a delta charge such as the O in water , or they could be neutral atoms with lone pairs such as N or O .

In the case of propionic acid the donor and acceptors are both on the propionic acid molecules. I have included a picture.

Please see p 204 and p. 205 of the thinkbook as well to help explain this further.

So why not methyl acetate?

methyl acetate Well there are no bonds between N, O, F or any high electronegative atom and H, only carbon has Hs attached! So there cant be hydrogen bonding occurring!!! There is no donor and with no donor there is no hydrogen bond to be had. Supplementary links:

http://www.oakland.k12.mi.us/Portals/0/Learning/IntermolecularForces.pdf http://www.bio.brandeis.edu/classes/biochem104/hydrogen_bonds.pdf http://www.chemguide.co.uk/atoms/bonding/hbond.html