Covalent bonds consist of shared pairs of electrons

A covalent bond forms when two atoms attain stable electron numbers in their outermost shells by sharing one or more pairs of electrons. Consider two hydrogen atoms coming close to one another, each with an unpaired electron in its single shell (Figure 2.5). When the electrons pair up, a stable association is formed, and this links the two hydrogen atoms in a covalent bond, forming the molecule H2.

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Figure 2.5 Electrons Are Shared in Covalent Bonds Two hydrogen atoms can combine to form a hydrogen molecule. A covalent bond forms when the electron orbitals of the two atoms overlap in an energetically stable manner.

A compound is a pure substance made up of two or more different elements bonded together in a fixed ratio. Chemical symbols identify the different elements in a compound, and subscript numbers indicate how many atoms of each element are present (e.g., H2O has two atoms of hydrogen bonded to a single oxygen atom). Every compound has a molecular weight that is the sum of the atomic weights of all atoms in the molecule. Looking at the periodic table in Figure 2.2, you can calculate the molecular weight of water to be 18.01. (But remember that this value comes from the average atomic weights of hydrogen and oxygen; the molecular weight of the heavy water in our opening story is higher because it is formed from heavier isotopes.) Molecules that make up living organisms can have molecular weights of up to half a billion.

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How are the covalent bonds formed in a molecule of methane gas (CH4)? The carbon atom has six electrons: two electrons fill its inner shell, and four unpaired electrons travel in its outer shell. Because its outer shell can hold up to eight electrons, carbon can share electrons with up to four other atoms—it can form four covalent bonds (Focus: Key Figure 2.6A). When an atom of carbon reacts with four hydrogen atoms, methane forms. Thanks to electron sharing, the outer shell of methane’s carbon atom is now filled with eight electrons, a stable configuration. The outer shell of each of the four hydrogen atoms is also filled. Four covalent bonds—four shared electron pairs—hold methane together. Focus: Key Figure 2.6B shows several different ways to represent the molecular structure of methane. Table 2.2 shows the covalent bonding capacities of some biologically significant elements.

focus: key figure

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Figure 2.6 Covalent Bonding Can Form Compounds (A) Bohr models showing the formation of covalent bonds in methane, whose molecular formula is CH4. Electrons are shown in shells around the nucleus. (B) Three additional ways of representing the structure of methane. In a structural formula, a covalent bond can be indicated with a single line or a shared pair of electron dots. The ball-and-stick model and the space-filling model show the spatial orientations of the bonds. The space-filling model indicates the overall shape and surface of the molecule. In the chapters that follow, different conventions will be used to depict molecules. Bear in mind that these are models to illustrate certain properties, not accurate portrayals of how atoms would actually appear.

Question

Q: Draw the four representations for carbon dioxide.

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table 2.2 Covalent Bonding Capabilities of Some Biologically Important Elements
Element Usual number of covalent bonds
Hydrogen (H) 1
Oxygen (O) 2
Sulfur (S) 2
Nitrogen (N) 3
Carbon (C) 4
Phosphorus (P) 5

STRENGTH AND STABILITY Covalent bonds are very strong, meaning that it takes a lot of energy to break them. At temperatures where life exists, the covalent bonds of biological molecules are quite stable, as are their three-dimensional structures. However, this stability does not preclude change, as you will see.

ORIENTATION For a given pair of elements—for example, carbon bonded to hydrogen—the length of the covalent bond is always the same. And for a given atom within a molecule, the angle of each of its covalent bonds, with respect to the other bonds, is generally the same. This is true regardless of the type of larger molecule that contains the atom. For example, the four filled orbitals around the carbon atom in methane are always distributed in space so that the bonded hydrogen atoms point to the corners of a regular tetrahedron, with carbon in the center (see Figure 2.6B). Even when carbon is bonded to four atoms other than hydrogen, this three-dimensional orientation is more or less maintained. The orientation of covalent bonds in space gives the molecules their three-dimensional geometry, and the shapes of molecules contribute to their biological functions (see Key Concept 3.1).

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Even though the orientations of bonds around each atom are fairly stable, the shapes of molecules can change. Think of a single covalent bond as an axle around which the two atoms, along with their other bonded atoms, can rotate.

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Bond rotation has enormous implications for the large molecules that make up living tissues. SInce long chains of atoms (especially carbons) can rotate freely, there are many possibilities for the arrangement of atoms within the chain. This allows molecules to alter their structures, for example, to fit other molecules.

MULTIPLE COVALENT BONDS Two atoms can share more than one pair of electrons, forming multiple covalent bonds. These can be represented by lines between the chemical symbols for the linked atoms:

UNEQUAL SHARING OF ELECTRONS If two atoms of the same element are covalently bonded, there is an equal sharing of the pair(s) of electrons in their outermost shells. However, when the two atoms are of different elements, the sharing is not necessarily equal. One nucleus may exert a greater attractive force on the electron pair than the other nucleus, so that the pair tends to be closer to that atom.

The attractive force that an atomic nucleus exerts on electrons is called its electronegativity. The electronegativity of an atom depends roughly on how many positive charges it has (atoms with more protons are more positive and thus more attractive to electrons) and on the distance between the nucleus and the electrons in the outer (valence) shell (the closer the electrons, the greater the electronegative pull). Table 2.3 shows the electronegativities (which are calculated to produce dimensionless quantities) of some elements important in biological systems. Note that oxygen (O) is very electronegative; in fact, oxygen is the second most electronegative element (after fluorine). Many organisms exploit the negativity of oxygen; moving electrons between C and O atoms powers living systems, as you will see in many subsequent examples in this text.

table 2.3 Some Electronegativities
Element Electronegativity
Oxygen (O) 3.5
Chlorine (Cl) 3.1
Nitrogen (N) 3.0
Carbon (C) 2.5
Phosphorus (P) 2.1
Hydrogen (H) 2.1
Sodium (Na) 0.9
Potassium (K) 0.8

If two atoms are close to one another in electronegativity, they will share electrons equally in what is called a nonpolar covalent bond. Two oxygen atoms, for example, each with an electronegativity of 3.5, will share electrons equally. So will two hydrogen atoms (each with an electronegativity of 2.1). But when hydrogen bonds with oxygen to form water, the electrons involved are unequally shared; they tend to be nearer to the oxygen nucleus because it is more electronegative than hydrogen. When electrons are drawn to one nucleus more than to the other, the result is a polar covalent bond (Figure 2.7).

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Figure 2.7 Water’s Covalent Bonds Are Polar These three representations all illustrate polar covalent bonding in water (H2O). When atoms with different electronegativities, such as oxygen and hydrogen, form a covalent bond, the electrons are drawn to one nucleus more than to the other. A molecule held together by such a polar covalent bond has partial (δ+ and δ) charges at different surfaces. In water, the shared electrons are displaced toward the oxygen atom’s nucleus.

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Because of this unequal sharing of electrons, the oxygen end of the hydrogen–oxygen bond has a slightly negative charge (symbolized by δ and spoken of as “delta negative,” meaning a partial unit of charge), and the hydrogen end has a slightly positive charge (δ+). The bond is polar because these opposite charges are separated at the two ends, or poles, of the bond. The partial charges that result from polar covalent bonds produce polar molecules or polar regions of large molecules. Polar bonds within molecules greatly influence the interactions they have with other polar molecules. Water (H2O) is a polar compound, and this polarity has significant effects on its physical properties and chemical reactivity, as you will see in later chapters.