The Silicate Minerals - Building blocks of rocks

Modified from Rocks and Minerals, The Silicate Minerals -- by Anne E. Egger, PH.D.

As we discussed in class, a mineral is a naturally occurring, inorganic, crystalline solid with diagnostic physical properties and a definite chemical composition. Rocks are typically composed of minerals although there are exceptions. As is always the case in nature, our definitions often do not cover all of the variables that are seen in nature. Some materials formed through geological processes are not composed of minerals yet are still considered rocks. Examples include obsidain and coal. We will be concentrating on rock-forming minerals as well as a few of the common accessory minerals found in the rocks we will be learning about. The mineral quartz (SiO2) is and example of a very common mineral. It is found in all rock types and in all parts of the world. It occurs as sand grains in sedimentary rocks, as crystals in both igneous and metamorphic rocks, and in veins that cut through all rock types, sometimes bearing gold or other precious metals. It is so common on Earth's surface that until the late 1700s it was referred to simply as "rock crystal." Today, quartz is what most people picture when they think of the word "crystal."

Quartz falls into a group of minerals called the silicates, all of which contain the elements silicon and oxygen in some proportion. Silicates are by far the most common minerals in Earth's crust and mantle, making up 95% of the crust and 97% of the mantle by most estimates. Silicates have a wide variety of physical properties, despite the fact that they often have very similar chemical formulas. At first glance, for example, the formulas for quartz (SiO2) and olivine ((Fe,Mg)2SiO4) appear fairly similar; these seemingly minor differences, however, reflect very different underlying crystal structures and, therefore, very different physical properties. Among other differences, quartz melts at about 600° C while olivine remains solid to temperatures of nearly twice that; quartz is generally clear and colorless, whereas olivine received its name from its olive green color.

The variety and abundance of the silicate minerals is a result of the nature of the silicon atom, and even more specifically, the versatility and stability of silicon when it bonds with oxygen. In fact, pure silicon was not isolated until 1822, when the Swedish chemist Jöns Jakob Berzelius finally succeeded in separating silicon from its most common compound, the silicate anion (SiO4)4-. This anion takes the shape of a tetrahedron, with an Si4+ ion at the center and four O2- ions at the corners (see Figure 1); thus, the molecular anion has a net charge of -4.

Figure 1a: Three ways of drawing the silica tetrahedron: a) At left, a ball & stick model, showing the silicon cation in orange surrounded by 4 oxygen anions in blue; b) At center, a space filling model; c) At right, a geometric shorthand.

Figure 1b: Silica tetrahedra we constructed in class. (image curtesy of L. Roy Bunnell)

 The Si-O bonds within this tetrahedral structure are partially ionic and partially covalent, and they are very strong. Silica tetrahedra bond with each other and with a variety of cations in many different ways to form the silicate minerals. Despite the fact that there are many hundreds of silicate minerals, only about 25 are truly common. Therefore, by understanding how these silica tetrahedra form minerals, you will be able to name and identify 95% of the rocks you encounter on Earth's surface.

Seeing the structure of the silicates

Early mineralogists grouped minerals according to physical properties, which spread the silicates across many groups because they have very different properties. By the early 1800s, however, Berzelius had begun classifying minerals based on their chemical composition rather than on their physical properties, defining groups such as the oxides and sulfides – and, of course, the silicates. At the time, Berzelius was able to determine the absolute proportions of elements within a mineral, but he could not see the internal arrangement of the atoms of those elements in their crystalline structure.

A detailed view of the internal arrangement of atoms within minerals would have to wait over 100 years for the development of X-ray diffraction (XRD) by Max von Laue, and its application to determine atomic distances by the father-son team of William Henry Bragg and William Lawrence Bragg a few years later. In the process of XRD, X-rays are aimed at a crystal. Electrons in the atoms within the crystal interact with the X-rays and cause them to undergo diffraction. In the same way that light can be diffracted by a grate or card (see Light I: Particle or Wave? module for more information on this topic), X-rays are diffracted by the crystal and a 2-dimensional pattern of constructive and destructive interference bands results. This pattern can be used to determine the distance between atoms within the crystal structure according to Bragg's Law (nλ = 2d sinΘ). The Braggs' work opened up a new world of mineralogy, and they were awarded a Nobel Prize in 1915 for their work determining the crystal structures of NaCl, ZnS, and diamond. XRD revealed that even minerals with similar chemical formulas could have very different crystal structures, strongly influencing those minerals' chemical and physical properties (e.g., diamond and graphite; calcite and aragonite; kyanite, andalusite, and sillimanite)

As scientists created XRD images of the atomic structure of minerals, they were better able to understand the nature of the bonds between atoms in the silicate and other crystals. Within a silica tetrahedron, any single Si-O bond requires half of the available bonding electrons of the O2- ion, meaning that each O2- may bond with a second ion, including another Si4+ ion. The result of this is that the silica tetrahedra can polymerize, or form chain-like compounds, by sharing an oxygen atom with a neighboring silica tetrahedron. The silicates are, in fact, subdivided based on the shape and bonding pattern of these polymers, because the shape influences the external crystal form, the hardness and cleavage of the mineral, the melting temperature, and the resistance to weathering. These different atomic structures produce recognizable and consistent physical properties, so it is useful to understand the structures at an atomic level in order to identify and classify the silicate minerals. Identifying minerals in a rock may seem like an arcane exercise, but it is only by identifying minerals that we begin to understand the history of a given rock.

The most common silicate minerals fall into four types of structures, described in more detail below: isolated tetrahedra, chains of silica tetrahedra, sheets of tetrahedra, and a framework of interconnected tetrahedra. The link below opens a page in a new window, which contains 3-dimensional versions of these different structures. You can manipulate and compare the structures as you read about them.

Comprehension Checkpoint

The silica tetrahedron is made up of

• a silicon atom surrounded by four oxygen atoms.
• an oxygen atom surrounded by four silicon atoms.

Isolated tetrahedra: Olivine

The simplest atomic structure involves individual silica anions and metal cations, usually iron (Fe) and magnesium (Mg), both of which exist most commonly as ions with charge of +2. Therefore, it takes two atoms of Fe2+ or Mg2+ (or one of each) to balance the -4 charge of the silica anion. Olivine (see Figures 2a and 2b below) is the most common silicate of this type, and it makes up most of the mantle. Because these minerals contain a relatively high proportion of iron and magnesium, they tend to be both dense and dark-colored. Because the tetrahedra are not polymerized, there are no consistent planes of internal atomic weakness, so they also have no cleavage. Garnet is another common mineral with this structure.

Figure 2a: Depiction of a single silicate tetrahedron.

Figure 2b: A picture of olivine (the green crystals), an example of a silicate structure composed of isolated tetrahedrons, with a vein of basalt (the gray material).

Figure 2c: Diagram of the structure of an olivine crystal, (Mg, Fe)2SiO4. (Image courtesy of Steven Earle)

Chains of tetrahedra: Pyroxenes and amphiboles

When silicate anions polymerize, they share an oxygen atom with a neighboring tetrahedron. Commonly, each tetrahedron will share two of its oxygen atoms, forming long chain structures. These chains still have a net negative charge, however, and the chains bond to metal cations like Fe2+, Mg2+, and Ca2+ to balance the negative charge. These metal cations commonly bond to multiple chains, forming bridges between the chains. Single-chain silicates include a common group called the pyroxenes, which are generally dark-colored (see Figures 3a, 3b, and 3c). Because the bonds within the tetrahedra are strong, planes of atomic weakness do not cross the chains; instead, pyroxenes have two cleavage planes parallel to the chains and at nearly right angles to each other (see Figures 3d and 3e).

Figure 3a: A schematic diagram of the single chain silica structure. Where two tetrahedra touch, they share an oxygen ion.

Figure 3b: Pyroxene is one of the dominant minerals in this sample of gabbro. It is the dark mineral and can be hard to recognize.

Figure 3c: A sample of a stubby pyroxene crystal showing the two cleavages 

at 90 degrees. Note the color is a green-black rather than a true black. 

Figure 3d: Because the bonds between the tetrahedra are strong planes of weakness do not cross the chains. The bonds between the cations (green spheres) and the chains are weaker. Thus, the cleavage planes are between the chains. (Image courtesy of Steven Earle)

Figure 3e: Pyroxene has two cleavages at 90 degrees due to the stacking of the single chains. 

(Image courtesy of Jeffery Gill Pittman)

Figure 3f: Single chain of silica tetrahedra constructed out of styrofoam balls 

like we constructed in class. (image curtesy of L. Roy Bunnell)

Double chains form when every other tetrahedron in a single chain shares a third oxygen ion with an adjoining chain (see Figure 4a). Like single chains, the double chains still maintain a net negativecharge and bond to cations that can form bridges between multiple double chains.

Figure 4a: A schematic diagram of the double chain silicate structure.

Double chain silicates, called amphiboles, host a wider variety of cations, including Fe2+, Mg2+, Ca2+, Al3+, and Na+, and have a wide variety of colors. The most common amphibole is hornblende (this is the one we have in the boxes we have in the lab), a black mineral found in igneous rocks like granite and andesite (see Figures 4b and 4c). Amphiboles tend to form prismatic crystals with two cleavage planes at 120 degrees to each other (see Figure 4d).

Figure 4b: Sample of hornblende. The wood-like
texture is visible in this sample. Note that the color is much
blacker than the sample of pyroxene above.

Figure 4c: Hornblende is the dark, bladed
crystals in this rock.

Figure 4d: Hornblende has two cleavages not at 90 degrees as a result of the stacking of its double chains. 

(Image courtesy of Jeffery Gill Pittman)

Pyroxenes and amphiboles (ex. hornblende) can be difficult to distinguish from one another, as they are both dark-colored, blocky minerals. A careful examination of the angle between cleavage planes, described above, is required to identify them. Pyroxene tends to be more blocky than hornblende which tends to be more bladed. Additionally, Pyroxene is typically a green-black whereas hornblende is very black with a wood-like surface texture.

Exercise: Oxygen Deprivation (courtesy of Steven Earle)
The diagram below represents a single chain in a silicate mineral. Count the number of tetrahedra versus the number of oxygen ions (yellow spheres). Each tetrahedron has one silicon ion so this should give the ratio of Si to O in single-chain silicates (e.g., pyroxene).

The diagram below represents a double chain in a silicate mineral. Again, count the number of tetrahedra versus the number of oxygen ions. this should give you the ration of Si to O in double chain silicates (e.g., hornblende).

Comprehension Checkpoint

The best way to tell single-chain silicate minerals from double-chain silicate minerals is by examining their

• color.
• cleavage planes.

Sheets: Micas and clays

When every tetrahedron shares three of its oxygen ions with neighboring tetrahedra, sheets are formed (see Figure 5a). Micas frequently exhibit perfect cleavage. This perfect cleavage results from the type of bonds that occur between sheets – van der Waals bonds. Because van der Waals bonds are weak, cleavage occurs between sheets, never across sheets. The micas muscovite and biotite (see Figure 5c and 5d) are both common sheet silicates, notable for their one perfect cleavage. Clay minerals such as kaolinite are another very important group of sheet silicate that incorporate water into their atomic structure. The presence of water lubricates the sheets and is what makes clay minerals easy to work with in forming pottery; the firing process heats the minerals to the point where the water is driven off, resulting in a rigid, durable structure such as a pot.

Figure 5a: A schematic drawing of the sheet silicate structure. This view is from above. (Image courtesy of Steven Earle)

Figure 5b: A molecular diagram of two micas, phlogopite on the left and muscovite on the right. The potassiums between the sheets are not strongly bonded to the sheets. Therefore, these minerals will cleave between the sheets. this is called sheet cleavage or basal cleavage, cleavage in only one direction. (Image courtesy of Stephen A. Nelson)

Figure 5c: An example of biotite.

Figure 5d: An example of muscovite. (Both biotite and muscovite are micas, which are one kind of sheet silicate.)

Framework: Quartz and feldspar

Figure 6a: An example of the 3-dimensional structure formed by a framework silicate

When each tetrahedron shares all of its oxygen atoms with adjacent tetrahedra, a very strong 3-dimensional framework of Si-O bonds is formed (see Figure 6a). Quartz is pure SiO2; note that thecharge is now exactly balanced and no other bonding ions are needed. In the feldspars, one or two out of every four Si4+ ions is replaced by an Al3+ ion, creating a charge imbalance that must be solved through the presence of additional cations: K+, Na+, and Ca2+. There are two kinds of feldspars upon which cations are incorporated into the structure. Feldspars that contain the K+ cation are called K-feldspars, or alkali feldspar, whereas those that contain Na+ and Ca2+ are called plagioclase feldspars (see Figure 6b). This separation occurs because K+ is a much larger cation than either Ca2+ or Na+, and its presence creates a slightly expanded framework structure.

Figure 6b: The white, blocky minerals in the rock on the left are plagioclase feldspar; the pink minerals in the rock on the right (granite) are K-feldspar.

Like olivine, quartz also has no cleavage, because there is no natural weakness within that 3-dimensional framework. The feldspars, on the other hand, have two good cleavage planes at ~90 degrees to each other, due in part to the way that the aluminum ion changes the structure slightly, opening up planes of weakness. Quartz and feldspar are generally light-colored as well, making them easily distinguishable from darker minerals like olivine and pyroxene.

Quartz and feldspar together make up the bulk of the rocks we see at the surface. Plagioclase feldspar is the single most common mineral in Earth's crust, making up an estimated 39% of both continental and oceanic crust. Quartz only makes up an estimated 12% of the entire crust, but it is by far the most common mineral we see on the surface because of its resistance to weathering.

Familiarity with these few minerals – olivine, garnet, pyroxene, hornblende, muscovite, biotite, K-feldspar, plagioclase, and quartz – prepares you to identify and interpret the vast majority of rocks you will see on Earth's surface.

Comprehension Checkpoint

Quartz has no cleavage because

• its framework structure has no natural weaknesses.
• it is identical in structure to feldspar.

Silicates as a natural resource

Though we generally think of coal or oil when discussing natural resources, silicate minerals are anatural resource we can't live without on our planet, and not just because of our increasing reliance on computers. Without quartz, there would be no glass. Without the clay minerals, we would have no ceramics or pottery. We use silicate minerals in the manufacture of many building materials, including bricks and concrete. The weathering of silicate minerals on the surface of Earth produces the soils in which we grow our foods and the sand on our beaches. The properties of the minerals that are important to us are based on the versatility of the silicate anion in combination with other elements.

Summary

Understanding the structure of silicate minerals makes it possible to identify 95% of the rocks on Earth. This module covers the structure of silicates, the most common minerals in the Earth's crust. The module explains the significance of the silica tetrahedron and describes the variety of shapes it takes. X-ray diffraction is discussed in relation to understanding the atomic structure of minerals.

Key Concepts

• Silicate minerals are the most common of Earth's minerals and include quartz, feldspar, mica, amphibole, pyroxene, and olivine.
• Silica tetrahedra, made up of silicon and oxygen, form chains, sheets, and frameworks, and bond with other cations to form silicate minerals.
• X-ray diffraction (XRD) allows scientists to determine the crystal structure of minerals.
• The physical properties of silicate minerals are determined largely by the crystal structure.

Now, take the quiz.