Scribd Logo
Upload

Welcome to Scribd!

  • 74 views

    Hydrogen Bonding: Where To Find Hydrogen Bonds?

    Uploaded by

    Rahul Dhiman
    Hydrogen bonding occurs when a hydrogen atom bonds to two other atoms - a donor atom X and an acceptor atom Y. The strength of hydrogen bonds depends on factors like the donor strength of X and acceptor capability of Y, as well as collective effects. Strong hydrogen bonds have some covalent character due to orbital overlap, while weak bonds are mainly electrostatic. The strength of donor and acceptor groups is governed by their electronegativity and ability to coordinate with other atoms. Hydrogen bonding plays an important role in determining the structures of compounds like water and ice.

    Copyright:

    © All Rights Reserved
    Download as PDF, TXT or read online from Scribd

    Hydrogen Bonding: Where To Find Hydrogen Bonds?

    Uploaded by

    Rahul Dhiman
    74 views28 pages
    Hydrogen bonding occurs when a hydrogen atom bonds to two other atoms - a donor atom X and an acceptor atom Y. The strength of hydrogen bonds depends on factors like the donor strength of X and acceptor capability of Y, as well as collective effects. Strong hydrogen bonds have some covalent character due to orbital overlap, while weak bonds are mainly electrostatic. The strength of donor and acceptor groups is governed by their electronegativity and ability to coordinate with other atoms. Hydrogen bonding plays an important role in determining the structures of compounds like water and ice.

    Original Description:

    vgcbdjvnvfmkgrvfmckgrfedfvbrvecmvecd

    Original Title

    h-bonding

    Copyright

    © © All Rights Reserved

    Available Formats

    PDF, TXT or read online from Scribd

    Did you find this document useful?

    Is this content inappropriate?

    Hydrogen bonding occurs when a hydrogen atom bonds to two other atoms - a donor atom X and an acceptor atom Y. The strength of hydrogen bonds depends on factors like the donor strength of X and acceptor capability of Y, as well as collective effects. Strong hydrogen bonds have some covalent character due to orbital overlap, while weak bonds are mainly electrostatic. The strength of donor and acceptor groups is governed by their electronegativity and ability to coordinate with other atoms. Hydrogen bonding plays an important role in determining the structures of compounds like water and ice.

    Copyright:

    © All Rights Reserved
    Download as PDF, TXT or read online from Scribd
    Download as pdf or txt
    74 views28 pages

    Hydrogen Bonding: Where To Find Hydrogen Bonds?

    Uploaded by

    Rahul Dhiman
    Hydrogen bonding occurs when a hydrogen atom bonds to two other atoms - a donor atom X and an acceptor atom Y. The strength of hydrogen bonds depends on factors like the donor strength of X and acceptor capability of Y, as well as collective effects. Strong hydrogen bonds have some covalent character due to orbital overlap, while weak bonds are mainly electrostatic. The strength of donor and acceptor groups is governed by their electronegativity and ability to coordinate with other atoms. Hydrogen bonding plays an important role in determining the structures of compounds like water and ice.

    Copyright:

    © All Rights Reserved
    Download as PDF, TXT or read online from Scribd
    Download as pdf or txt
    You are on page 1of 28

    Hydrogen bonding

    Where to find hydrogen bonds? 1


    Hydrogen bonding

    WHAT IS A HYDROGEN BOND?


    A hydrogen bond exists when a hydrogen atom is bonded to two
    or more other atoms, a donor atom X and an acceptor atom Y.
    Since the hydrogen atom has only one orbital (1s) at sufficiently
    low energy, hydrogen bonds are mainly electrostatic in nature
    but covalent and repulsive orbital-orbital interactions are also
    present.
    Depending on the type of X and Y, there are strong and weak
    hydrogen bonds.
    In the case of weak and very weak hydrogen bonds, hydrogen
    bonding is mainly electrostatic in nature.
    In the case of strong and very strong hydrogen bonds, covalent
    bonding phenomena are also of some importance.
    This means that hydrogen bonds are something special.

    2
    Hydrogen bonding

    Hydrogen bonds
    in
    solid H2O (weak)
    and HF (strong)

    The strongest hydrogen bonds are formed to the most


    electronegative elements
    3
    Hydrogen bonding

    Enthalpies of some hydrogen bonded systems and transitions


    4
    Hydrogen bonding

    Normal boiling points of p-block binary hydrogen compounds


    5
    Hydrogen bonding
    is directed by the lone pairs of the acceptor atom(s) Y

    Gas-phase hydrogen-bonded complexes formed with HF and


    lone pair orientation as indicated by VSEPR theory

    6
    Hydrogen bonding
    for Y = O this leads to

    The crystal structure of ice. The large H2O cages in the clathrate hydrate
    cycles represent O atoms. The H atoms Cl2.(H2O)7.25. O atoms occupy
    are placed between the O atoms. intersections H atoms the lines.

    Structure building of hydrogen bonds

    7
    Hydrogen bonding

    Types and structure building of hydrogen bonds

    8
    Hydrogen bonding

    Types and structure building of hydrogen bonds


    (intra and intermolecular hydrogen bonds)

    9
    Hydrogen bonding

    Structure building of hydrogen bonds


    10
    Hydrogen bonding

    Structure building of hydrogen bonds

    11
    Hydrogen bonding

    Configuration/coordination of water molecules of crystallization


    12
    Hydrogen bonding

    (a) Cl—H…………...…Cl (b) F……....H……..F


    137 185 pm 113 113

    Potential energy curves for X-H…X bonds with


    (a) double-minimum for weak and (b) single-minimum for strong H-
    bonds
    13
    Hydrogen bonding

    Infrared spectra of pure (bottom) and diluted (top) Isopropanol


    showing the shift and the broadening of the O-H stretching band by
    hydrogen bonding
    14
    Hydrogen bonding
    How to investigate/characterize hydrogen bonds?

    By systematic investigation of isotypic compounds


    (e.g. Oxohydrates MXO3.nH2O (X = S, Se, Te), M(HSeO3)2.nH2O)
    with X-ray and neutron diffraction, NMR, IR, Raman, INS

    15
    Hydrogen bonding
    How to investigate/characterize hydrogen bonds?

    By systematic investigation of isotypic compounds


    and correlation of the structural, spectroscopic and theoretical data16
    Hydrogen bonding

    νOH δH2O νSO3 δSO3

    17
    Hydrogen bonding

    18
    Hydrogen bonding

    19
    Hydrogen bonding

    δH2O νSO δSO3


    νOD

    νOH

    H2O librations

    20
    Hydrogen bonding

    IR spectra and νOD/d(O…O) relations of some salt hydrates 21


    Hydrogen bonding

    WHAT IS A HYDROGEN BOND?


    A hydrogen bond exists when a hydrogen atom is bonded to two or more
    other atoms. Since the hydrogen atom has only one orbital (1s) at
    sufficiently low energy, hydrogen bonds are mainly electrostatic in nature
    but covalent and repulsive orbital-orbital interactions are also present.
    The strength of hydrogen bonds is governed by
    (i) the inherent hydrogen bond donor strength (acidity) of the hydrogen
    atom and the acceptor capability of the respective acceptor group,
    (ii) collective effects, as cooperative, competitive, and synergetic effects,
    which increase or decrease the inherent donor strengths and acceptor
    capabilities,
    (iii) structural features, as the number of acceptor groups, e. g. two-center,
    three-center (bifurcated), etc. hydrogen bonds, and the hydrogen bond
    angles X−H...Y and H...Y−Z built by the donor (X), acceptor (Y), and H
    atoms (linear or bent), and
    (iv) packing effects and constraints of the respective crystal structure.

    22
    Hydrogen bonding

    STRENGTH OF HYDROGEN BONDS


    In the case of weak and very weak hydrogen bonds, the respective
    bonding is mainly electrostatic in nature with attractive and repulsive
    charge-charge, charge-dipole, charge-induced dipole, and charge-
    multipole interactions between the partially positive charged hydrogen
    atom and the negative charged areas of the acceptor atom Y.
    In the case of strong and very strong hydrogen bonds, in addition to the
    Coulomb forces, covalent bonding phenomena via orbital-orbital overlap
    attractive and closed-shell repulsive forces are of some importance.

    23
    Hydrogen bonding

    STRENGTH OF HYDROGEN BONDS


    The strength of hydrogen bonds in inorganic solids is governed by both
    the hydrogen-bond donor strength of the hydrogen-bond donor X and the
    hydrogen-bond acceptor capability of the hydrogen-bond acceptor Y.
    For the formation of hydrogen bonds two rules have been established:
    (i) All hydrogen-bond acceptors available in a molecule will be engaged
    in hydrogen bonds as far there are available donors.
    (ii) The hydrogen-bond acceptors will be saturated in order of decreasing
    strength of the hydrogen bonds formed.
    Both the hydrogen-bond donor strengths and the hydrogen-bond
    acceptor capabilities, are modified by additional phenomena like the
    synergetic, the cooperative, and the anti-cooperative or competitive
    effects. The various effects are highly non-additive.

    24
    Hydrogen bonding

    Hydrogen-bond donor strength and acceptor capability


    The synergetic effect describes the increase of the strength of a hydrogen
    bond through metal ions coordinated to the donor atom X.
    The cooperative effect means the increase of the donor strength of a
    hydrogen-bond donor if the donor concurrently acts also as acceptor for a
    second hydrogen bond.
    The anti-cooperative or competitive effect means the decrease of the strength
    of hydrogen bonds due to the decrease of
    (i) the donor strength e.g. through coordination (donor competitive effect) or
    (ii) the acceptor capability (acceptor competitive effect) of the entities
    involved in the respective hydrogen bonds.
    Both may be caused by the different coordination of the donor and acceptor
    atoms X and Y.

    25
    Hydrogen bonding
    Hydrogen-bond donor strength and acceptor capability
    The acceptor capability primarily depends on the gas-phase basicity of the
    hydrogen-bond acceptor groups to hydrogen atoms. It is modified by the
    acceptor competitive effect due to the coordination and bond strength of the
    acceptor atom Y, e.g. by
    (i) the receipt of more than one hydrogen bonds,
    (ii) the total number of atoms coordinated to the acceptor atom,
    (iii) the strength of the Y−Z bonds of the hydrogen-bond acceptor group, and
    (iv) the deviation from the most favorable hydrogen-bond acceptor angle H…Y−Z.
    In the case of O−H…Y hydrogen bonds, the relative acceptor capability range as
    ClO4- < NO3- < BrO3- < IO3- < I- < Br- < H2O < Cl- < < SO42- < SeO42- < SO32- <
    SeO32-< PO43- < F- < OH- (hydrogen-bond acceptor series).
    The donor strengths of common hydrogen-bond donors range as OH- < SH- <
    NH2- < NH3 < H2O < HSeO3- < H5-nIO6n- < H3O+. It is governed by both the
    positive partial charge at the acid hydrogen atom, and the strength and
    hybridization of the X−H bond of the donor molecule. The donor strength is
    increased due to the cooperative and the synergetic effects and decreased due to
    the anti-cooperative/donor competitive effect.
    26
    Hydrogen bonding

    Hydrogen-bond donor strength and acceptor capability


    In the case of the synergetic effect, i. e., bonding of the donor atom X to metal
    atoms, the X−H bonds of the donor are both weakened and polarized with
    increasing strength of the respective M−X bonds and, hence, the acidity of the
    respective hydrogen atom and the donor strength are increased.
    The synergetic effect increases with increasing charge and decreasing size
    of the respective metal ions as well as with increasing covalence of the M−X
    bonds. The latter is particularly strong in the case of Cu2+, Zn2+, and Pb2+ ions.
    In the case of the cooperative effect, the X−H bond of the hydrogen-bond
    donor is weakened because the donor atom X acts concurrently as hydrogen-
    bond acceptor and hydrogen-bond donor, and, hence, acidity and donor
    strength of the respective hydrogen atom are increased.

    27
    28

    You might also like