Water: prankster of the natural world part 1

If you’ve ever taken a life sciences course your teacher probably mentioned one of several properties that make water particularly interesting. Water is cohesive meaning it sticks to itself, adhesive meaning it sticks to other things (superhydrophobic surfaces notwithstanding), and is considered the “universal solvent” because it readily dissolves many other substances. These properties are some of the most critical that allow water to function as the key to most terrestrial forms of life. Another interesting fact about water is that it is one of the few substances that exists in all three states of matter (solid, liquid and gas) in fairly non-extreme locals on earth. Furthermore, these phases exist within a relatively narrow range of temperatures – the entire transformation from solid to gas spans only 100 degrees Celsius (from melting of ice at 0 °C to boiling of liquid water at 100 °C). Compare that to ethyl alcohol (the alcohol in “alcoholic” beverages) which solidifies at -114 °C  and boils at 78 °C (a range of only about 200 °C, but with freezing occurring at a temperature below the coldest temperature ever recorded on earth) or a pure metal like iron with a melting temperature of 1538 °C and boiling temperature of 2862 °C  – that’s a phase range of over 1000 °C!

It is important at this point in my introduction to define a phase: a phase is one of several atomic or molecular configurations for a given composition. When considering melting and boiling points, we are observing only the transition between the three states of matter mentioned above, however it is equally correct to consider multiple crystal structures for one composition of solid as different phases. Some of these solid phases are not easily distinguishable without sophisticated analytical techniques, while others have characteristic changes in physical properties.  No one would confuse graphite and diamond though they are in fact different phases of the same element. Plasma, also known as a superheated gas, is considered a fourth phase of matter but not one normally observed in nature with a notable exception being bolts of lightning. However, when heated to the point of being a plasma the atoms defining a given composition become ionized and for this reason plasma is normally considered separate from the more conventional states of matter. Fun fact for gamers: this is the plasma in all your favorite late game super-weapons.

This is where things get weird for our old friend agua.

Consider the following scenarios:

1) Two identical pans are pre-heated to temperatures above the boiling point of water. The first pan is heated to 150 °C and the second pan to 300 °C. If drops of water at room temperature are placed into each pan, which drop will undergo the phase change from liquid to gas (boil) first?

 

2) Two identical containers of water (same volume, same container size and material) are placed into a freezer. One container contains water at just below its’ boiling point (< 100 °C) and the other at roughly room temperature (21 °C). Which will freeze first?

 

If considering only the energetics of each scenario, the logical conclusion is that a higher temperature pan means faster boiling, and a lower starting temperature means faster solidification. But if you were to perform these exact experiments at home (which I hope you do!) the opposite would occur.

 

So whats going on? Is water playing by the rules (of thermodynamics)? Fortunately for us, Gibbs will remain stationary in his grave. As it turns out, both of these scenarios are good examples of how the properties of matter can change dramatically after a phase change. In both of these cases, variations in heat transfer between phases is likely to blame.

 

For the water in the pan scenario, there exists a temperature above which water is so quickly vaporized upon hitting the pan a thin layer of steam is trapped below the liquid droplet, causing it to literally levitate above the surface of the pan on cushion of water vapor. Think air hockey table, but droplets of boiling water replacing the plastic puck. This temperature is called the “Leidenfrost point”, which according to unreferenced figure from Wikipedia is about 200 °C. Steam has a thermal conductivity roughly 10-100 times lower than that of liquid water depending on the temperature. In an idealized example, thermal conductivity is a measure of how easily a quantity of heat in a high temperature region can travel from one side of a 100% dense (no porosity) slab of material to the other. Thermal conductivity has units of energy per length per degree per second (Joules/(meter*°C*seconds)), meaning for a fixed length and temperature a material with lower thermal conductivity will take more time than a material with higher thermal conductivity to transfer the same amount of energy.

At temperatures above the Leidenfrost point the Leidenfrost effect is observed and drops of water on a pan will take longer to boil because the steam trapped below the liquid water takes more time to transfer heat to the droplet from the pan. The videos below demonstrate drops of water into a pan below (top) and above (bottom) the Leidenfrost point. Above the Leidenfrost point, the droplets can barely be heard to sizzle as they zoom around on cushions of steam. For the pan heated above the Leidenfrost point, occasional contact with the edges of the pan, which are actually at a lower temperature or placing drops repeatedly in the same area which leads to local cooling will lead to momentary sizzling as the entire droplet boils. For the videos below, I used a nonstick pan and an eyedropper to put a few drops of tapwater onto the pan at a time. For the lower temperature I set my range to setting of 2 out of 10 and for the higher temperature I set it to about 6 out of 10 and waited a few minutes at each temperature for the pan to heat up.

 

 

You may have heard of ole’ Leidenfrost’s namesake before associated with dipping things (namely one’s hand) into boiling lead after placing it in water. The Myth Busters did it after significant deliberation and preliminary testing, but somehow the alpha geeks at PopSci seemed to think it would make a good “DIY” project. I have to say, I can understand why dipping digits is the sexier version of the Leidenfrost effect demonstration, but the pan + water trick seems a little less invasive. In their defense, PopSci also covered this demo and the equivalent effect with boiling Nitrogen instead of steam as well.

However you plan to enjoy the Leidenfrost effect, do so under proper supervision and be careful.

Check out part 2 for a discussion on the second scenario!

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

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  Timothy Durham was convicted of rape when a test showed his DNA genotype matched the DNA recovered from the crime scene. Eye witnesses testified that Durham was in a different state at the time of the incident, but he wasn’t exonerated from his 3000 year sentence until follow up DNA analysis showed that the preliminary forensic analysis used in the trial was misinterpreted (Thomas et al.). DNA testing serves an invaluable part in our criminal justice system, but it comes with complications and bias that can lead to wrongful convictions and misinformed juries.  

Background:

Forensic genetics aims to identify the origin of a biological sample. It can be traced back to Karl Landsteiner who discovered human ABO blood groups. With blood groups, suspects could be eliminated based on their blood type. For example, if a suspect had type A blood and there was type B blood left at the scene by the perpetrator, the investigators could rule out the suspect. Unfortunately, the reverse didn’t work. If the suspect and perpetrator both had the same blood type, it can’t be concluded that the suspect was guilty. Blood identifiers evolved into 8 distinct categories which improved the ability to eliminate suspects, but could only conclude that (if the system matched) it might be the perpetrator or this person might be related to the perpetrator (Jobling and Gill). The field evolved in the 1980s with the discovery of Minisatellites, lines of repetitive DNA that don’t encode proteins. Minisatellite patterns in DNA create what we know today as the DNA fingerprint, and it has a much higher accuracy rate than previous methods (Augustyn et al.). Around the same time, a breakthrough for victims of sexual assault was discovered. In the case of assault, bodily fluids of both the victim and the assaulter can get mixed. A process called differential lysis was created which could selectively increase the concentration of sperm in a fluid sample thereby allowing for accurate DNA testing (Jobling and Gill). Forensics evolved to use single-locus probe testing after several years because of its ease of interpretation. It looked at specific minisatellites that had high variability between subjects. This was the first DNA-based method to be used in a criminal investigation. Two murder homicides from several years apart were connected using DNA evidence. The evidence was then used to exonerate an innocent man, and the guilty party was found when he tried to evade mandatory DNA testing for all men in the small town. His guilt was then reinforced when the DNA profiles matched, and he gave a confession (Jobling and Gill). Finding DNA at a crime scene doesn’t guarantee that you’ll find a murderer. There are issues with non-pure samples and limited samples that make DNA work difficult, and accreditation of facilities and new techniques and take time (Jobling and Gill).  

Subjectivity of DNA Interpretation:

In a 2009 publication, the National Academy of Science discusses the possibility for subjective influence in lab based forensics. The interpretation bias happens in complex cases where, for example, there could be a mixture of DNA. A study published in 2011 looked specifically at this issue. A gang rape happened in Georgia, and the mixture in DNA from the case was used to prosecute one suspect after another suspect took a plea bargain to testify against him. With DNA mixtures, there are three possible conclusions: suspect excluded, suspect cannot be excluded, and inconclusive. If the suspect is excluded, it means that there’s little to no possibility that his DNA is part of the sample. If the suspect cannot be excluded, it means that there’s a possibility that his DNA is part of the sample. In the trial, the DNA examiners who knew the context of the case concluded that the suspect being prosecuted could not be excluded. The 2011 study gave the DNA evidence from this case and the DNA profiles of the suspects to 17 forensic examiners. These examiners had no context of the case, and they all worked independently. Of the 17, only 1 came to the same conclusion (suspect cannot be excluded) as the examiners who knew the context of the case. Twelve of the 17 concluded that the suspect who was prosecuted and convicted had no relation to the DNA found in the sample. Not only does this show that subjectivity occurs due to the context of the case, but the 17 examiners came up with different findings based on their past experiences meaning that not all DNA analysis is objective. Some organizations like the Scientific Working Group on DNA Analysis Methods say that quantitative statistical evidence should be presented with every categorical conclusion, but the US doesn’t require this (Dror and Hampikian).

False Positives:

There are two categories that cause wrongful identification in a DNA report: coincidental matches and false positives. Coincidental matches are DNA matches between two unrelated people. The probability of these matches is about 1 to 500,000 for white individuals and about 1 to 350,000 for black individuals. This small probability of coincidental matches makes people feel confident in DNA evidence. False positives, on the other hand, are matches between DNA and test DNA that result from issues in the forensics lab. There have been multiple cases of forensics labs accidentally switching victim and suspected rapist DNA which lead to convictions that were later overturned when the lab realized the error. There are also cases of misreading or misunderstanding a sample. In a case from 1993, a man was convicted of rape because someone interpreted a mixed sample of victim and perpetrator DNA as an individual sample. The conviction was again overturned. To prevent false convictions, retesting DNA is allowed, but it’s not an efficient solution. Many people are pushing for statistical information on the probability of false positives, so that the jurors can make accurate judgements based on DNA evidence (Thomas et al.).  

Conclusion:

DNA analysis is a useful tool for the criminal justice system, but subjectivity can be an issue in forensic testing. To combat wrongful convictions, there are organizations like The Innocence Project who use DNA testing to free the innocent, but reformed forensic testing standards should be put in place to prevent subjectivity and to ensure juries are correctly informed during trials. https://www.innocenceproject.org/    

Citation:

Augustyn , Adam, et al. “DNA Finerprinting.” Encyclopedia Britannica , 26 Apr. 2018, www.britannica.com/science/DNA-fingerprinting#ref153186. Dror, Itiel E., and Greg Hampikian. “Subjectivity and Bias in Forensic DNA Mixture Interpretation.” Science & Justice, vol. 51, no. 4, 2011, pp. 204–208., doi:10.1016/j.scijus.2011.08.004. Jobling, Mark A., and Peter Gill. “Encoded Evidence: DNA in Forensic Analysis.” Nature Reviews: Genetics, vol. 5, no. 10, Oct. 2004, pp. 739–751., doi:10.1038/nrg1455. Thompson, William C, et al. “How the Probability of a False Positive Affects the Value of DNA Evidence.” Journal of Forensic Sciences, vol. 48, no. 1, Jan. 2003, pp. 1–8., doi:10.1520/jfs2001171.