Showing posts with label Scientific Reasoning. Show all posts
Showing posts with label Scientific Reasoning. Show all posts

Friday, November 17, 2023

Why Do Metals Conduct Electricity?

 

Why Do Metals Conduct Electricity?


Have you ever wondered why metals conduct electricity? Perhaps you’ve wondered why metals (and water) are some of the only electrical conductors you encounter in daily life?

In this post, I will explain why metals are such good electrical conductors, and also explain how nonmetals like water and glass can also become conductors.

Metals conduct electricity because they have “free electrons.” Unlike most other forms of matter, metallic bonding is unique because the electrons are not bound to a particular atom. This allows the delocalized electrons to flow in response to a potential difference. 

Metallic Bonding

I’m going to be honest, I never fully understood metallic bonding until grad school (do I even understand it now??)

In high school and undergrad, any time I saw a question about metallic bonding, the answer was always “because metallic bonding has a sea of electrons.” So the short answer is “metals conduct electricity because they have a sea of delocalized electrons that are free to leave as soon as they feel a voltage.”

What does that mean? And why do metals have this “sea of electrons” when other materials don’t?

Because of quantum interactions, metal atoms all share their outer electron. Rather than electrons orbiting a specific atom, the electrons roam all over the group of metal atoms. It is kinda like super-covalent bonding–instead of sharing electrons between 2 atoms, they are shared among all the atoms.

The “electron sea model” is the best way to describe this phenomena. As you’ve probably learned, the metal atoms are aligned in a repeating pattern (a crystal structure), and the space between and around these atoms are filled with electrons that can freely move.

Just as metal ions give up electrons to a different atom in ionic bonding, the metal ions give up those same electrons to the electron sea in metallic bonding. Na+ means that a piece of sodium will have 1 electron in the electron sea, per Na atom. Al3+ means that aluminum metal will have 3 free electrons per aluminum atom. If you’re interested, this video illustrates the electron sea model and more.

Metallic bonding holds together because of electrostatic forces: each atom is positively charged and the negatively charged “sea” acts like glue that binds atoms together. 

This bonding is why metals have so many shared properties, such as 

  • malleability
  • ductility
  • high melting point (especially true for transition metals)
  • strength
  • shininess
  • thermal conductivity
  • and electrical conductivity

Basically, metallic bonding is a unique type of bonding, arising from quantum-mechanical effects, that makes metals act like metals.

There is a lot of heavy math you can use to prove why metals have delocalized electrons, but at certain point, I just have to say: 

Perhaps a more intuitive way to understand metallic bonding is by looking at band diagrams.

Band Gap

Band diagrams can help us understand conductors, semiconductors, and insulators. There are many features of the band diagram that are important to semiconductors, but for this article, you only need to know the band gap.

The band diagram shows the possible energy states for an electron. For a single element and electron, there are some very specific energy levels that the electron can exist in. If the energy is energized it can hop between these states, and if there is enough energy it’s even possible for the electron to leave the atom completely.

As you have a piece of metal with a terrifyingly large number of atoms and electrons, these allowed energy states for each atom basically merge into a “band” of continually allowed states. This is called the valence band

Beyond the valence band is the conduction band. The conduction band is the collection of energy states where the electrons have enough energy to leave the atom that they’re bound to.

The band gap is the distance between these valence bands and conduction bands. The difference between metals, insulators, and semiconductors is the size of the band gap.

Metals have no band gap. In other words, the conduction band and valence band overlap, so an atom is not bound to any particular atom. If it has enough energy to leave, it just leaves.

Semiconductors have a small band gap
This means that if the electrons don’t have enough energy to fully jump across the band gap, the semiconductor does not conduct at all. If there is enough energy to pass this barrier, the material conducts. Semiconductors are super useful because they can act as switches, either passing 0% or 100% of the current.

Insulators have a large band gap.
The distinction between insulator and semiconductor is a bit nebulous–it’s not like scientists have a simple value and if the band gap is larger than that value, it’s an insulator. These terms are practical–anything which is considered an insulator has a band gap that is too large to cross in a realistic scenario. Trying to pass too much current through many insulators will destroy the material before electrons have enough energy to jump across the band gap.

Type of MaterialMaterialBand Gap (eV)
SemiconductorSi
Ge
GaN
GaP
GaAs
1.12
0.67
3.44
2.26
1.43
Insulatordiamond
PE (polyethylene)
SiO2
5.47
8.8
8.9

Electrical Properties of Metals

The main electrical property is electrical conductivity.

Conductivity measures the amount of electrical current a material can carry. It can also be called “specific conductance” and  is the inverse of resistivity.

Conductivity is given by the following equation.

n is the carrier density–in other words, how many electrons exist per cross-sectional area.

q is the electric charge of each carrier–for electrons, this is -1.

\mu is the mobility, which is how quickly the electron can move through the material.

This equation was generalized for any situation involving electrical conductivity (including ion conduction), but in most cases the charge carrier is just electrons.

 So conductivity is basically just how many electrons can squeeze through the wire in a given amount of time.

Usually, if engineers can change the conductivity of something, they are changing \mu, the mobility of electrons. For example, grain boundaries can scatter electrons, reducing the speed they travel through the wire. Precipitates and alloying elements reduce conductivity for the same reason.

Some examples of high and low conductivity metals are given in the table below.

Top 5 metals with the highest
electrical conductivity
Conductivity σ x 106
at 20°C (S/m)
Silver (Ag)63.0
Copper (Co)59.6
Gold (Au)41.1
Aluminum (Al)37.7
Calcium (Ca)29.8
Top 5 metals with the lowest
electrical conductivity
Conductivity σ x 106
at 20°C (S/m)
Manganese (Mn)0.69
Mercury (Hg)1.02
Titanium (Ti)2.38
Lead (Pb)4.55
Niobium (Nb)7.00

Electrical Conductivity of Metals vs Temperature

The opposite of conductivity is resistivity (or resistance). Resistivity is the intrinsic version of resistance.

  $$\sigma = \frac{1}{\rho}$$

As temperature increases metals increase in resistivity (or decrease in conductivity).

Increases in temperature causes a linear decrease in metals’ conductivity because of phonon-electron interactions. Since temperature is a measure of how quickly the atoms vibrate (we can call this vibration a “phonon”), increased vibration can interact with electrons passing through.

This impedes the electrons’ movement and reduces the electron mobility. 

A very different logic applies to semiconductors!

\mu


In fact, mobility is so important to resistance that at absolute zero, when lattice vibrations cease and electrons can pass through a metal unimpeded, metals can  become superconductors.

Ways to Change a Metal’s Electrical Conductivity

There are many ways engineers can modify the electrical conductivity of metals, from changing the metal’s environment to grain boundary modification.

Shape

Shape is probably what you learned in high school, regarding conductivity. This doesn’t really change a materials intrinsic resistivity, but it does affect the extrinsic resistance.

Since resistance is the electrons that pass per cross sectional area, you can calculate resistance by multiplying resistivity by length of the wire, and dividing by the wire’s cross sectional area.

Materials engineers don’t deal with resistance as much as resistivity, but it’s an important relationship to know. Especially because increased resistance can change the temperature, which can affect resistivity

Temperature

We talked about temperature a bit earlier, but here’s another graph showing how temperature affects resistivity of metals.

The table below shows resistivity coefficient values for different metals. 

Elementα x 10-3 (1/oC)
Aluminum (Al)3.8
Copper (Co)4.29
Iron (Fe)6.41
Mercury (Hg)8.9
Nickel (Ni)6.41
Platinum (Pt)3.93
Silver (Ag)1.59
Tin (Sn)4.2
Tungsten (W)4.5

Because increasing the metal atoms’ vibration causes electrons to interact with the atoms more, conductivity decreases as temperature decreases. And, in a perfect crystal at absolute zero, atom vibrations cease and metals become superconducting.

Impurity Atoms

For a similar reason as temperature, increasing impurity atoms reduces conductivity because it decreases the electron mobility. When alloying elements in solid solution, the base metal element forms a lattice structure. Most of the atoms in the lattice are the same kind, but in alloys, there are additional elements that can replace the base element (this is called a substitutional solid solution).

Since these other elements are a different size than the base element, they strain the lattice, decreasing conductivity.

Even small alloying additions can have a large effect on conductivity. For example, adding 0.2 wt% of aluminum to copper can decrease the copper’s conductivity by 20%.

Here is a quick graph showing how resistivity changes as impurity elements are added copper.

Even if additional elements don’t form a solid solution, the alternative (precipitates) will also decrease conductivity, although the relationship depends on the exact precipitate. In many cases, precipitates decrease conductivity less than solid solution atoms, so one quick method of determining precipitation in metals is by checking its conductivity. 

Grain Boundaries

The fourth way that engineers can control conductivity is by changing grain boundaries. Grain boundaries are portions of a metal where two crystal arrangements with a different orientation come together.

As you might expect from the other points, grain boundaries have lattice strain which interacts with electrons, reducing their mobility. Fewer grain boundaries means increase resistance.

Why Does Water Conduct Electricity? (Ion Conduction)

Unlike metals, which conduct electricity by “free electrons,” water conducts electricity by moving charged ions.

An ion is an atom with a net positive or negative charge.

For example, if you took table salt (NaCl) and dissolved it in water, the salt would dissociate into Na+ and Cl. Na basically steals an electron from Cl.

In its regular state, these ions are just spread randomly around the water.

When water experiences a potential change, however, the free-floating ions can move. Since positive ions are attracted to a negative charge, and negative ions are repulsed by a negative charge, if you dipped one end of a live wire into a salted bathtub, the electrons in the wire would repulse the Cl ions and attract the Na+ ions.

The net flow of charged atoms is what causes electricity to flow through atoms. The electrons themselves are not actually moving. (Technically, there are actually half reactions occurring: 2e + H2O —> 2OH + H2 and 2Cl –> Cl2 + 2e which means that eventually, the water will use up all the ions and stop conducting).

And yes, this means that pure water is not a good conductor. Sea water is about a million times more conductive than pure water, and a hundred times more conductive than drinking water. 

However, since regular drinking water usually has ions dissolved in it (from metal, or minerals), drinking water is still around 10,000 times more conductive than pure water.

Final Thoughts

You learned about how metals are an array of positively charged atoms, held together by “electron glue” which is shared between all the atoms. This sea of electrons occurs because of quantum mechanical effects that give metals no bandgap. In fact, “no bandgap” is probably the best way to define metals.

Using the conductivity equation

  $$\sigma = \frac{1}{\rho} = nq\mu$$

you saw that this sea of electrons gives metals a very large n value, because there are lots of free electrons. You also learned how engineers can influence the conductivity of a metal by changing the electron mobility.

Finally, you learned why water “conducts” electricity even though it’s not a metal!

I hope this post has answered all your questions about electrical conductivity in metals!

Why Mercury is Used in Thermometers (and Modern Alternatives)

 

Why Mercury is Used in Thermometers (and Modern Alternatives)


While modern thermometers are usually filled with dyed alcohol, mercury is a better liquid to use. Well, as long as you don’t count mercury’s health hazards.

Nowadays, mercury thermometers are rare. But why was mercury so common before people cared about the health effects?

Mercury was used in thermometers primarily because of its liquid temperature range, its constant coefficient of thermal expansion, and its high thermal conductivity. However, nowadays, mercury is usually banned because of its health hazards.

Why Mercury is a Great Thermometer Filling

Mercury is an ideal thermometer filling for 5 reasons:

1. Mercury is a liquid from -39 ºC to 357 ºC. 

Few materials can be liquid in a similar range–and mercury is the only pure metal that is liquid at room temperature. Many of the other benefits I list would apply to most metals, but being a solid is a dealbreaker!

Mercury’s wide temperature range makes it much more versatile–you can use the same thermometer to measure a person’s body temperature, check how cold the weather is, and even measure the temperature of cooked food.

In certain alloys (such as with Thallium), the freezing point of mercury can be dropped even further.

2. Mercury has a large, linear coefficient of thermal expansion.

Although you probably learned in high school that thermal expansion is always linear, that’s not always true. Thermal expansion is actually approximated with polynomials, and the linear approximation is the simplest.

The large thermal expansion is good because it allows the thermometer reading to be determined more easily. The linear approximation is less important because it would be possible to draw a thermometer with a non-linear scale, but that’s a lot of effort.

As you can see, mercury’s coefficient of thermal expansion is not only linear, it barely changes with respect to temperature. Ethanol (current replacement of mercury) changes linearly with temperature, and water changes nonlinearly.

3. Mercury is easy to see because it is reflective.

Yes, you can take other materials and dye them, but the dye may affect thermal expansion. It’s not a bad solution (and it’s the most common current solution), but mercury’s natural reflectivity is a point in its favor.

4. Mercury Conducts Heat Well.

Good thermal conductivity means that the thermometer will have the correct temperature, faster.

5. Mercury doesn’t “Wet” Glass

Wetting refers to the way that a liquid sticks to a solid. You can see how much a liquid wets a solid by putting a drop of the liquid on a flat surface of the solid.

Since mercury is non-wetting to glass, it sticks to itself more than the glass. Water sticks to the glass a bit more.

In a thermometer, if the liquid wets the glass, then falling temperature will cause the liquid to stick to the glass, showing a higher measurement than reality.

Summary Chart

Among the obvious liquids to fill a thermometer, mercury has the best combination of properties. Its thermal expansion barely changes over temperature, which makes measurement very accurate. Mercury is liquid under all temperatures where it is safe for humans, and it has a high-enough thermal conductivity to enable quick temperature measurements.

Element/CompoundLiquid Range
(ºC )
Thermal Expansion
(1/ºC)
Thermal Conductivity
(W/(m-K))
Mercury-39- 357Low and linear8.4
Water0 – 100High and nonlinear0.609
Ethanol-114 – 78Medium and linear0.171
Gallium30 – 240040.6

Gallium is an interesting replacement for mercury, but since it’s solid below 30ºC, it’s not ideal for measuring the weather. It is possible to make alloys with a lower melting point than gallium, such as gallinstan.

However, colored ethanol is the most-common material in liquid thermometers today, because it’s cheap. If you wanted a “better” thermometer, your money is better spent buying a non-liquid thermometer, rather than using an expensive fusible alloy. But if you are interested in other applications for low-melting point metals, you might want to check out my article about gallinstan and other fusible alloys.

Why Mercury is No Longer Used in Thermometers

Well, perhaps I should say they should no longer be used in thermometers. Government regulations around the world have put restrictions to stop this practice. In many places, mercury thermometers are completely forbidden.

Mercury is extremely toxic. It’s so toxic, in fact, pollutants (of all kinds) can build up trace amounts in fish, and humans who eat too much of this fish can even suffer mercury poisoning.

If mercury builds up inside animals (including humans), the animals cannot get rid of the heavy metal. Scientists have disputed whether amalgamous dental fillings pose a risk of mercury poisoning, but broken mercury-filled thermometers definitely pose a risk of mercury poisoning.

Not only is mercury poisoning from broken thermometers dangerous because of accidents, mercury is mesmerizing to play with and many children have intentionally broken thermometers to play with the raw mercury inside.

Surprisingly, inhaling vapor from the mercury is actually more dangerous than swallowing it. So don’t try playing with mercury; even a careful adult who knows not to swallow mercury may accidentally inhale it.

For these safety reasons, mercury is no longer used in thermometers. There are still applications that require mercury (and also face increasing regulation), but thermometers are especially dangerous because they are a common household object which can easily release pure liquid mercury.

Alternatives to Mercury-based Thermometers

There are many ways of determining the temperature, besides mercury-filled thermometers.

Colored Water

Honestly this is a bad choice. Water wets the glass and is not useful for reading temperatures below 0 ºC or above 100 ºC. It also has a very nonlinear coefficient of thermal expansion. Water-based thermometers could be used for reading body temperature, but that’s about it.

Colored Ethanol

Colored ethanol is the standard liquid thermometer filling these days. Ethanol is cheap and has a very low freezing point, but it boils at a lower temperature than water. It also wets glass. Ethanol thermometers are good for reading body temperature or the weather, but not for cooking.

Gallinstan

One liquid metal alloy that is similar to mercury is gallinstan, which is a eutectic alloy of gallium, indium, and tin. The eutectic allows gallinstan to reach a lower melting point than any of its constituent pure elements. Gallinstan still has a higher freezing point than mercury, however, so in most cases that require a more expensive thermometer, it’s better to go with a non-liquid option.

Springs

Meat thermometers often use a (solid) metal spring to determine temperature. Since these are used exclusively at high temperature and accuracy is not that important, the comparatively low thermal expansion of a solid metal is not a big issue.

Bimetallic Strips

Bimetallic strips are mostly used in thermostats. These have two metals connected together with different thermal expansions. As the temperature changes, one piece of metal will expand/contract more than the other, causing the strip to bend. Depending on the direction that it bends, the thermostat will trigger cooling or heating in your home.

Thermocouple

If you are a scientist, you’ve probably used a thermocouple. These are among the most accurate devices for reading temperature, and rely on measuring the resistivity change of a metal as an electric current goes through it (it’s a bit more complicated, but that’s the simple version).

Digital thermometers usually use a thermocouple.

Infrared Sensor

These devices are usually not super accurate, but they have many advantages (you can use them from a distance, and they are very fast). All objects with thermal energy radiate that energy–which typically falls in the infrared spectrum. Infrared sensors detect this infrared spectrum, compare it to the surrounding background spectrum, and calculate the temperature.