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List of The Glades episodes
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The Glades is a one-hour drama that ran on A&E from July 11, 2010 to August 26, 2013. The premiere was the highest rated episode of an original series to be shown on A&E.[1]
The show's premise involves a Chicago detective taking a South Florida job with the Florida Department of Law Enforcement, which he believes will afford a more relaxing lifestyle, but he finds things are more complicated than he imagined.
A total of 49 episodes of The Glades were produced and aired over four seasons.
Contents
[hide]
1 Series overview
2 Episodes
2.1 Season 1 (2010)
2.2 Season 2 (2011)
2.3 Season 3 (2012)
2.4 Season 4 (2013)
3 References
4 External links
Series overview[edit]
Season
Episodes
Originally aired
First aired
Last aired
1 13 July 11, 2010 (2010-07-11) October 3, 2010 (2010-10-03)
2 13 June 5, 2011 (2011-06-05) September 5, 2011 (2011-09-05)
3 10 June 3, 2012 (2012-06-03) August 12, 2012 (2012-08-12)
4 13 May 27, 2013 (2013-05-27) August 26, 2013 (2013-08-26)
Episodes[edit]
Season 1 (2010)[edit]
No. in
series
No. in
season
Title
Directed by
Written by
Original air date
Production
code
U.S. viewers
(million)
1
1 "Pilot" Peter O'Fallon Clifton Campbell July 11, 2010 (2010-07-11) BDF179 3.55[2]
After being exiled to Palm Glade, Florida, for supposedly sleeping with his captain's wife, ex-Chicago cop Jim Longworth handles his first case with the state police. He investigates the case of a headless woman who was found in a lake, even going as far as to pester his golf partner Carlos, the medical examiner on the case, while also developing a relationship with his nurse, Callie.
2
2 "Bird in the Hand" Peter O'Fallon Matt Witten July 18, 2010 (2010-07-18) BDF101 3.35[3]
While Longworth spends more time with Callie's son, he finds an abandoned airplane with a dead body inside.
3
3 "A Perfect Storm" Timothy Busfield Alfonso H. Moreno July 25, 2010 (2010-07-25) BDF104 2.92[4]
Longworth gets caught up in a murder investigation that appears to be a spree killing just as a hurricane hits Palm Glade.
4
4 "Mucked Up" Randall Zisk Elle Johnson August 1, 2010 (2010-08-01) BDF102 3.29[5]
The corpse of a businessman emerges from the muck in a sugar cane field days before the big football game.
5
5 "The Girlfriend Experience" Tim Hunter Lee Goldberg & William Rabkin August 8, 2010 (2010-08-08) BDF103 3.10[6]
Longworth gets a nightmarish call that Carlos has been found dead lying on a bed of fishes, but it turns out that it wasn't Carlos, just a man who had stolen his identity. Meanwhile, Callie deals with some tax problems.
6
6 "Doppelganger" Guy Ferland Story by : Matt Witten
Teleplay by : David J. Burke August 15, 2010 (2010-08-15) BDF105 2.80[7]
A man suffering from head trauma claims to have witnessed a murder before being attacked and believes the murderer looks exactly like him.
7
7 "Cassadaga" Bill Eagles Alfonso H. Moreno August 22, 2010 (2010-08-22) BDF106 3.32[8]
Longworth and Carlos investigate the murder of a psychic adviser in the town of Cassadaga, where a former psychic predicts that a close friend of Longworth's will die.
8
8 "Marriage Is Murder" Jonathan Frakes Tom Garrigus August 29, 2010 (2010-08-29) BDF107 3.08[9]
A ruthless divorce attorney is murdered. Meanwhile Callie's son, Jeff claims to have seen a man standing at his window, but Callie believes he's imagining it. Believing Jeff is telling the truth, Jim has the boy look at mugshots on the computer, through which Jeff finds out the truth about his father's criminal past and confronts his mom.
9
9 "Honey" Colin Bucksey Elle Johnson September 5, 2010 (2010-09-05) BDF108 3.21[10]
Jim Longworth's latest case sends him to the famed Native American-owned Blues Rock Casino, a high-end gambling establishment filled with millions of dollars of rock 'n' roll memorabilia. When the head of the casino, a tribal elder, crashes through a skylight and lands on a roulette table, Longworth must figure out who is behind her mysterious death. Was it suicide or foul play? Jim's first hurdle is getting the smart and sexy Josie Tigertail, a tribal police officer, to allow the Florida Department of Law Enforcement to run point on the investigation. Meanwhile, Callie convinces herself she just wants to be friends with Longworth, but then is surprised when feelings of jealousy overtake her upon seeing Longworth interact with Josie.
10
10 "Second Chance" Tricia Brock Tom Garrigus September 12, 2010 (2010-09-12) BDF109 3.08[11]
A dead man in a swimming pool leads Longworth and Carlos to a Pompano Beach mansion, and then into the world of high-end horse breeding. Callie, who was once an aspiring jockey, becomes Longworth's secret weapon in the case as she shows him the ins and outs of this competitive and cut-throat world. Callie shows Jim a side of her he's never seen and the two grow closer than ever before.
11
11 "Booty" Elodie Keene Lee Goldberg & William Rabkin September 19, 2010 (2010-09-19) BDF110 2.93[12]
A famed treasure-hunter is murdered, and the attention is immediately turned to the victim's famous uncle Big Jack Hasker, a legendary treasure hunter and adventurer. Longworth dives into this world of treasure hunting and discovers the victim was hot on the trail to uncovering the mythic Spanish ship, the Magdalena, which is believed to contain billions of dollars of booty. If Longworth can figure out whether or not the victim was actually close to uncovering the prize, maybe he will be able to find the real killer. While working the case, Longworth discovers Callie's passion for treasure hunting lore and guided by her passion and expertise, the two embark on an adventure that could change their lives forever.
12
12 "Exposed" Gary A. Randall Alfonso H. Moreno September 26, 2010 (2010-09-26) BDF111 2.73[13]
The death of a young woman puts Jim at odds with a powerful political family when it appears she was having an affair with a Florida State Senator. Complicating matters is the senator's wife, who will do whatever it takes to protect her husband's political career and her family's name.
13
13 "Breaking 80" Dennie Gordon Matt Witten & Alfonso H. Moreno October 3, 2010 (2010-10-03) BDF112 2.69[14]
A man who was recently released from prison is found dead along the fairway. The man was the caddy and life-long friend of professional golfer Scott Winters. Longworth discovers the victim may have served time for a crime he didn't commit.
Season 2 (2011)[edit]
No. in
series
No. in
season
Title
Directed by
Written by
Original air date
Production
code
U.S. viewers
(million)
14
1 "Family Matters" Gary A. Randall Tom Garrigus June 5, 2011 (2011-06-05) BDF201 3.01[15]
The daughter of a Cuban mobster is murdered, and Jim must solve the case while preventing a war between rival mob families. Callie prepares for Ray's release from jail, and tells Jim she wants to be with him, yet promises Ray to hold off on a divorce for three months. Manus warns Jim a complaint has been filed regarding his relationship with Callie, and advises Jim to allow the family to solve their problems.
15
2 "Old Ghosts" Lee Rose Clifton Campbell & Alfonso H. Moreno June 12, 2011 (2011-06-12) BDF202 2.61[16]
Jim hunts a serial killer from Chicago with the help of detective Samantha Harper, who Callie learns is his former lover. Manus offers Callie a job with the FDLE as a forensic nurse.
16
3 "Lost and Found" Kelly Makin Clifton Campbell & Kim Newton June 19, 2011 (2011-06-19) BDF204 2.39[17]
An incident at a slumber party and a missing baby are the concerns of the day. Callie joins the FDLE as a forensic nurse.
17
4 "Moonlighting" Jonathan Frakes Elle Johnson June 26, 2011 (2011-06-26) BDF203 2.53[18]
The body of a mechanic leads to an investigation involving NASCAR; when Ray is attacked in front of Jeff, Callie considers witness protection.
18
5 "Dirty Little Secrets" Timothy Busfield Story by : John Mankiewicz
Teleplay by : Clifton Campbell & Elle Johnson & John Mankiewicz July 10, 2011 (2011-07-10) BDF205 2.80[19]
A dead man in a bathroom stall leads to a posh rehab facility. Carlos balances work, play and family. Callie and Jeff carry on with Ray gone.
19
6 "Gibtown" Jeff Bleckner Alfonso H. Moreno July 17, 2011 (2011-07-17) BDF206 2.57[20]
A town of circus sideshow performers becomes a town of suspects in a murder. Callie and Jim come to terms on what their relationship means. Sam considers taking a job with the FDLE.
20
7 "Addicted To Love" Jeremiah Chechik Tom Garrigus & Clifton Campbell July 24, 2011 (2011-07-24) BDF207 2.40[21]
A dead Haitian doctor leads to black market prescription meds.
21
8 "Second Skin" Tricia Brock Lois Johnson July 31, 2011 (2011-07-31) BDF208 2.59[22]
A man is found poisoned by snakes in a church.
22
9 "Iron Pipeline" Eric Laneuville Alfonso H. Moreno & Clifton Campbell August 7, 2011 (2011-08-07) BDF209 2.26[23]
Jeff's mentor, the high school soccer coach, is found shot dead on campus.
23
10 "Swamp Thing" Timothy Busfield Tom Garrigus August 14, 2011 (2011-08-14) BDF210 2.89[24]
Clues to a murder are found because of a poached animal. Jim and Callie restart their relationship.
24
11 "Beached" Artie Mandelberg Karen Hall August 21, 2011 (2011-08-21) BDF211 2.64[25]
A love triangle leads to murder. Callie has some big news for Jim.
25
12 "Shine" Jon Terlesky Story by : Shaz Bennett
Teleplay by : Elle Johnson August 28, 2011 (2011-08-28) BDF212 2.71[26]
Bootleggers may have murdered a man on a themed booze cruise. Someone from Callie's past comes back with big news and it could threaten her relationship with Jim, the hospital, and the FDLE.
26
13 "Breakout" Kelly Makin Elle Johnson & Tom Garrigus & Alfonso H. Moreno September 5, 2011 (2011-09-05) BDF213 2.38[27]
Two brothers, former inmates, take Callie's hospital hostage.
Season 3 (2012)[edit]
No. in
series
No. in
season
Title
Directed by
Written by
Original air date
Production
code
U.S. viewers
(million)
27
1 "Close Encounters" Jeff Bleckner Tom Garrigus June 3, 2012 (2012-06-03) BDF301 3.11[28]
A young couple discover an older man's dead body, after they see what they perceive to be a UFO.
28
2 "Poseidon Adventure" Lee Rose Elle Johnson June 10, 2012 (2012-06-10) BDF302 2.90[29]
A lifeguard clears the beach when he thinks he has seen a shark fin in the water, until after closer inspection it is revealed the fin actually belongs to a dead woman in a mermaid costume. Jim encourages Callie to take a head nurse job in Atlanta. Even though they will be apart, he assures her things will work out.
29
3 "Longworth's Anatomy" Randy Zisk Wendy Battles June 17, 2012 (2012-06-17) BDF303 2.53[30]
Carlos performs an autopsy for Daniel's classmates, then dismisses them when he discovers that the victim did not die as reported. Jim helps Callie set up her residence in Atlanta where she reveals how much she misses him. She later falls asleep with his shirt under her head.
30
4 "The Naked Truth" Eric Laneuville Lisa Henthorn June 24, 2012 (2012-06-24) BDF304 3.11[31]
A nude woman's body is found under an overturned boat on a riverbank, leading the team to the nearby Swan Lake nudist colony. Jennifer flirts with Jim, telling him that she has to keep her eyes on him.
31
5 "Food Fight" Ron Underwood Dailyn Rodriguez July 1, 2012 (2012-07-01) BDF305 2.50[32]
Carlos, Jennifer, and Jim go to lunch and find the owner of a food truck dead. Jim visits Callie to boost her mood. She then pours her heart out to him.
32
6 "Old Times" Kelly Makin Lee Goldberg & William Rabkin July 8, 2012 (2012-07-08) BDF306 3.19[33]
Joggers find a woman's dead body. She had been stabbed eight times and her body moved to the site. Although the episode begins with Jim and Callie in bed together, it ends with him having dinner with Jennifer.
33
7 "Public Enemy" Lee Rose Elle Johnson July 15, 2012 (2012-07-15) BDF307 3.37[34]
Three boys playing football decide to check out a neighborhood house they have been curious about. They find the owner dead on the porch. Jim promises to help Callie in her tax case.
34
8 "Fountain of Youth" Gary A. Randall Tom Garrigus July 22, 2012 (2012-07-22) BDF308 3.18[35]
A supermodel's dead body is found in a pool at a spa. Jim and Callie profess their love for each other.
35
9 "Islandia" Emile Levisetti Dailyn Rodriguez August 5, 2012 (2012-08-05) BDF309 3.09[36]
A $130 million lottery winner is found murdered. Autopsy shows trauma to the head and a poison in his system. Jim and Callie's communication suffers as she must study for her exam.
36
10 "Endless Summer" Jeff Bleckner Story by : Shaz Bennett
Teleplay by : Wendy Battles August 12, 2012 (2012-08-12) BDF310 3.10[37]
The founder a new surf clothing line is discovered murdered just as she was to offer an endorsement to a young, local surfing champion. Jim proposes to Callie, even though she has passed her board exam and may move to Atlanta.
Season 4 (2013)[edit]
No. in
series
No. in
season
Title
Directed by
Written by
Original air date
Production
code
U.S. viewers
(million)
37
1 "Yankee Dan" Emile Levisetti Dailyn Rodriguez May 27, 2013 (2013-05-27) BDF401 3.26[38]
Jim and Carlos investigate the murder of a woman at an old haunted plantation. Callie gives Jim an answer to his proposal.
38
2 "Shot Girls" Jonathan Frakes John J. Sakmar & Kerry Lenhart June 3, 2013 (2013-06-03) BDF402 2.74[39]
The body of a spokesmodel washes up on the beach and Jim investigates the prominent rum brand that employed her. Callie and Jeff pack for her move back to Florida.
39
3 "Killer Barbecue" Paul Edwards Tom Garrigus June 10, 2013 (2013-06-10) BDF403 2.31[40]
An owner of a large BBQ business is found dead at a BBQ cook-off. Daniel teams up with his brother Drew to win the same BBQ cook-off.
40
4 "Magic Longworth" Donna Deitch Matthew J. Lieberman June 17, 2013 (2013-06-17) BDF404 2.31[41]
Jim and Carlos look into the death of a male entertainer.
41
5 "Apocalypse Now" Marc Roskin Elle Johnson June 24, 2013 (2013-06-24) BDF405 2.56[42]
Jim and the FDLE search for the body of a disappearing 10K Zombie run coordinator.
42
6 "Glade-iators!" Martha Coolidge John J. Sakmar & Kerry Lenhart July 1, 2013 (2013-07-01) BDF406 2.55[43]
The body of a prestigious bank VP mysteriously appears in the bank's vault. Jim discovers that the victim was not such a delicate dame after all.
43
7 "Gypsies, Tramps and Thieves" Ron Underwood Tom Garrigus July 8, 2013 (2013-07-08) BDF407 2.51[44]
A ritualistically decorated crime scene sends Jim and Carlos in search of Floridian gypsies. Jeff leaves Florida to see his dad while Michael Longworth, Jim's dad, drops by for a visit.
44
8 "Three's Company" Eric Laneuville Matthew J. Liberman July 15, 2013 (2013-07-15) BDF408 2.40[45]
Mitch Buckner, a financial planner, is found dead in a house that he was looking to buy. Michael informs Jim that he and his mother are divorcing.
45
9 "Fast Ball" Ron Underwood Elle Johnson July 29, 2013 (2013-07-29) BDF409 2.38[46]
A towel boy finds professional jai alai player Lori Aest's body in a laundry bin at an arena.
46
10 "Gallerinas" Eric Laneuville Dailyn Rodriguez August 5, 2013 (2013-08-05) BDF410 2.32[47]
Texas oil billionaire and art collector Richard Harris Crawford's body falls out of a crate.
47
11 "Civil War" Kelly Makin John J. Sakmar & Kerry Lenhart August 12, 2013 (2013-08-12) BDF411 2.31[48]
Assistant state's attorney Ethan Russell is found dead near a Civil War re-enactment.
48
12 "Happy Trails" Gary A. Randall Shaz Bennett August 19, 2013 (2013-08-19) BDF412 2.69[49]
A dead cowboy is found with a shotgun wound in his chest and a circle with a "G" in the middle branded into his chaps.
49
13 "Tin Cup" Randy Zisk Tom Garrigus August 26, 2013 (2013-08-26) BDF413 3.41[50]
A man's body, dressed for play on a golf course, is found on a mini-golf course. Since Jim's wedding day is two days away, Manus wants to give the case to someone else. He insists on taking it. Callie's son Jeff surprises her by showing up for the wedding. The attendees are getting worried about Jim not showing up. He has been shot twice in the chest at their new home.
References[edit]
Jump up ^ Gorman, Bill (July 12, 2010). "A&E's Series Premiere Of 'The Glades' Is Most Watched Original Drama Series Telecast In Network History". TV By the Numbers. Retrieved July 13, 2010.
Jump up ^ Gorman, Bill (July 13, 2010). "Sunday Cable Ratings: True Blood, Leverage, Kate Plus 8 & Much More". TV By the Numbers. Archived from the original on July 15, 2010. Retrieved August 17, 2010.
Jump up ^ Seidman, Robert (July 20, 2010). "Sunday Cable Ratings: True Blood, Leverage, The Glades, Kourtney & Khloe & More". TV By the Numbers. Archived from the original on July 23, 2010. Retrieved July 20, 2010.
Jump up ^ Seidman, Robert (July 27, 2010). "Sunday Cable Ratings: True Blood, Entourage, The Glades, Kourtney & Khloe & More". TV By the Numbers. Archived from the original on July 29, 2010. Retrieved July 27, 2010.
Jump up ^ Seidman, Robert (August 3, 2010). "Sunday Cable Ratings: 'The Glades Rises;' 'True Blood' Hits a 3.0 Adult 18-49 Rating & Much More". TVbytheNumbers.com. TV By the Numbers. Archived from the original on August 5, 2010. Retrieved August 3, 2010.
Jump up ^ Seidman, Robert (August 10, 2010). "Sunday Cable Ratings: 'The Glades,' 'True Blood' Steady, 'Rubicon' Goes Unnoticed & Much More". TV By the Numbers. Retrieved August 17, 2010.
Jump up ^ Seidman, Robert (August 17, 2010). "Sunday Cable Ratings: 'True Blood, Kourtney & Khloe, Hasslehoff Roast;' + 'The Glades' Slips & More". TV By the Numbers. Archived from the original on August 19, 2010. Retrieved August 17, 2010.
Jump up ^ Seidman, Robert (August 24, 2010). "Sunday Cable Ratings: 'True Blood, Rubicon, Mad Men, Kardashians' & More". TV By the Numbers. Retrieved August 24, 2010.
Jump up ^ Seidman, Robert (August 31, 2010). "Sunday Cable Ratings: More Records for True Blood + The Glades, Rubicon, Mad Men & More". TV By the Numbers. Archived from the original on September 3, 2010. Retrieved September 20, 2010.
Jump up ^ Seidman, Robert (September 8, 2010). "Sunday Cable Ratings: The Glades Down a Little; Rubicon, Mad Men Moreso". TV By the Numbers. Retrieved September 20, 2010.
Jump up ^ Gorman, Bill (September 14, 2010). "Big Sunday For Cable Ratings: True Blood, VMAs, Jersey Shore, Iron Chef, Kardashians & Lots More". TV By the Numbers. Retrieved September 20, 2010.
Jump up ^ Seidman, Robert (September 21, 2010). "Sunday Cable Ratings: 'Boardwalk Empire' Premieres; 'Rubicon' Still Struggling + The Glades, Mad Men, Kardashians & Lots More". TV By the Numbers. Retrieved September 26, 2010.
Jump up ^ Gorman, Bill (September 28, 2010). "Sunday Cable Ratings: 'Boardwalk Empire' Falls; 'Rubicon' Stays Low + Glades, Mad Men, Kardashians, Dexter & Lots More". TV By the Numbers. Archived from the original on October 5, 2010. Retrieved October 4, 2010.
Jump up ^ Seidman, Robert (October 5, 2010). "Sunday Cable Ratings: 'Boardwalk Empire' Mostly Stable; 'Rubicon' Still Tiny; Mad Men, Kardashians, Dexter & Lots More". TV By the Numbers. Archived from the original on October 10, 2010. Retrieved October 7, 2010.
Jump up ^ Gorman, Bill (June 7, 2011). "Monday Cable Ratings: 'Pawn Stars' Tops Night; Plus 'WWE Raw,' 'Secret Life,' NHL Stanley Cup Finals, 'American Pickers' & More". TV by the Numbers. Retrieved June 8, 2011.
Jump up ^ Gorman, Bill (June 14, 2011). "Sunday Cable Ratings: 'Game of Thrones', 'Real Housewives,' 'Kardashians,' 'In Plain Sight,' 'Army Wives' & More". TV by the Numbers. Retrieved June 22, 2011.
Jump up ^ Seidman, Robert (June 21, 2011). "Sunday Cable Ratings: 'Falling Skies,' 'Game of Thrones', 'The Killing,' 'In Plain Sight,' 'Law & Order: CI,' 'The Glades' and Much More". TV by the Numbers. Retrieved June 22, 2011.
Jump up ^ Seidman, Robert (June 28, 2011). "Sunday Cable Ratings: More 'True Blood' & 'Falling Skies,' + 'Kardashians,' 'Law & Order: CI,' 'The Glades' and Much More". TV by the Numbers. Retrieved June 28, 2011.
Jump up ^ Seidman, Robert (July 12, 2011). "Sunday Cable Ratings: 'True Blood' Bounces Back, 'Falling Skies' Steady + Women's World Cup, 'In Plain Sight,' 'The Glades' & More". TV by the Numbers. Retrieved July 12, 2011.
Jump up ^ Seidman, Robert (July 19, 2011). "Sunday Cable Ratings: 'True Blood' Slips , 'Falling Skies' Steady + 'Breaking Bad,' 'Leverage,' 'In Plain Sight,' 'The Glades' & More". TV by the Numbers. Archived from the original on July 19, 2011. Retrieved July 19, 2011.
Jump up ^ Seidman, Robert (July 26, 2011). "Sunday Cable Ratings: 'True Blood' Rises, 'Falling Skies' Steady + Kardashians, 'Entourage,' 'Breaking Bad,' 'Leverage,' 'The Glades' & Much More". TV by the Numbers. Retrieved July 26, 2011.
Jump up ^ Seidman, Robert (August 2, 2011). "Sunday Cable Ratings: 'True Blood,' Shark Week , 'Falling Skies,' 'In Plain Sight,' 'Breaking Bad,' 'Leverage,' & Much More". TV by the Numbers. Retrieved August 2, 2011.
Jump up ^ Seidman, Robert (August 9, 2011). "Sunday Cable Ratings: 'True Blood,' Kardashians, 'Falling Skies,' 'In Plain Sight,' 'Breaking Bad,' & Much More". TV by the Numbers. Retrieved August 11, 2011.
Jump up ^ Seidman, Robert (August 16, 2011). "Sunday Cable Ratings: 'True Blood' Rises, Leads Night + Kardashians, 'Entourage,' 'Leverage,' 'Breaking Bad,' & Much More". TV by the Numbers. Retrieved August 23, 2011.
Jump up ^ Seidman, Robert (August 23, 2011). "Sunday Cable: 'True Blood,' 'Kardashians,' 'Entourage' Lead + 'Breaking Bad,' 'Glee Project' & Much More". TV by the Numbers. Retrieved August 23, 2011.
Jump up ^ Gorman, Bill (August 30, 2011). "Sunday Cable : 'Video Music Awards,' 'True Blood,' 'Kardashians,' 'Entourage,' 'Breaking Bad,' 'Leverage' & Much More". TV by the Numbers. Retrieved September 2, 2011.
Jump up ^ Gorman, Bill (September 5, 2011). "Monday Cable: 'Pawn Stars' Back On Top, 'Kardashians' Finale, 'The Closer,' 'Rizzoli & Isles,' 'WWE RAW' & More - Ratings". TV by the Numbers. Retrieved September 5, 2011.
Jump up ^ Kondolojy, Amanda (June 5, 2012). "Sunday Cable Ratings: NBA Playoffs + 'Game of Thrones' Finale, MTV Movie Awards, 'Sister Wives', 'The Glades', 'Longmire' + More". TV by the Numbers. Retrieved June 5, 2012.
Jump up ^ Bibel, Sara (June 12, 2012). "Sunday Cable Ratings: 'True Blood' Wins Night, 'Mad Men', 'Longmire', 'The Client List', 'The Glades', 'Drop Dead Diva' & More". TV by the Numbers. Retrieved June 12, 2012.
Jump up ^ Bibel, Sara (June 19, 2012). "Sunday Cable Ratings: 'True Blood', 'Falling Skies', 'Real Housewives of NJ', 'Keeping up with the Kardashians' + NASCAR & More". TV by the Numbers. Retrieved June 19, 2012.
Jump up ^ Bibel, Sara (June 26, 2012). "Sunday Cable Ratings: 'True Blood' Wins Night, 'Falling Skies', 'Real Housewives of New Jersey', 'The Newsroom', 'Army Wives' ,'The Glades' & More". TV by the Numbers. Retrieved June 27, 2012.
Jump up ^ Kondolojy, Amanda (July 3, 2012). "Sunday Cable Ratings: 'BET Awards' + 'True Blood', European Football, 'Keeping Up With the Kardashians', 'Real Housewives of NJ' & More". TV by the Numbers. Retrieved July 4, 2012.
Jump up ^ Bibel, Sara (July 10, 2012). "Sunday Cable Ratings: 'True Blood' Wins Night, 'Keeping Up With the Kardashians', 'Falling Skies', 'Army Wives', 'The Newsroom', 'Drop Dead Diva', 'Longmire', 'Walking Dead Marathon' & More". TV by the Numbers. Retrieved July 11, 2012.
Jump up ^ Kondolojy, Amanda (July 17, 2012). "Sunday Cable Ratings: 'True Blood' Beats 'Breaking Bad' Premiere, + 'Keeping Up With the Kardashians', 'Very Funny News', 'Real Housewives of New Jersey', 'Falling Skies' & More". TV by the Numbers. Retrieved July 18, 2012.
Jump up ^ Bibel, Sara (July 24, 2012). "Sunday Cable Ratings: 'True Blood' Wins Night, 'Breaking Bad', 'Falling Skies', 'Army Wives', 'The Newsroom', 'Longmire' & More". TV by the Numbers. Retrieved July 24, 2012.
Jump up ^ Bibel, Sara (August 7, 2012). "Sunday Cable Ratings:'True Blood' Wins Night, 'Keeping Up With the Kardashians', 'Falling Skies', 'Breaking Bad', 'Army Wives', 'Leverage'& More". TV by the Numbers. Retrieved August 7, 2012.
Jump up ^ Kondolojy, Amanda (August 14, 2012). "Sunday Cable Ratings: 'True Blood' Beats 'Comedy Central Roast of Roseanne' + 'Falling Skies', NASCAR, 'Army Wives' & More". TV by the Numbers. Retrieved August 15, 2012.
Jump up ^ Bibel, Sara (May 29, 2013). "Monday Cable Ratings:NBA Playoffs Win Night, 'WWE Raw', 'Love & Hip Hop', 'Longmire', 'Hit the Floor', 'The Glades' & More". TV by the Numbers. Retrieved May 30, 2013.
Jump up ^ Kondolojy, Amanda (June 4, 2013). "Monday Cable Ratings:NBA Basketball Dominates + 'Love & Hip Hop', 'Monday Night RAW', NHL Hockey, 'Teen Wolf' & More". TV by the Numbers. Retrieved June 5, 2013.
Jump up ^ Bibel, Sara (June 11, 2013). "Monday Cable Ratings: 'Love & Hip Hop' Wins Night, 'WWE Raw', 'Teen Wolf', 'Major Crimes' , 'Switched at Birth', 'Longmire' & More". TV by the Numbers. Retrieved June 12, 2013.
Jump up ^ Kondolojy, Amanda (June 18, 2013). "Monday Cable Ratings: 'Love and Hip Hop: Atlanta' Wins Night + NHL Stanley Cup, 'WWE Raw', 'Fast N Loud', 'Hit The Floor' & More". Retrieved June 19, 2013.
Jump up ^ Bibel, Sara (June 25, 2013). "Monday Cable Ratings: 'Love & Hip Hop Atlanta' Wins Night, 'WWE Raw', 'Teen Wolf', 'Major Crimes', 'Longmire', 'Switched at Birth', 'Warehouse 13' & More". TV by the Numbers. Retrieved June 26, 2013.
Jump up ^ Kondolojy, Amanda (July 2, 2013). "Monday Cable Ratings:'Love and Hip Hop' Wins Night + 'Monday Night RAW', 'Hit the Floor', 'Fast N Loud', 'Real Housewives of OC' + More". TV by the Numbers. Archived from the original on June 26, 2015. Retrieved July 3, 2013.
Jump up ^ Bibel, Sara (July 10, 2013). "Monday Cable Ratings: 'Love & Hip Hop' Leads + 'WWE RAW,' 'Switched at Birth,' 'Major Crimes,' 'Longmire' & More". TV by the Numbers. Archived from the original on June 26, 2015. Retrieved July 11, 2013.
Jump up ^ Kondolojy, Amanda (July 16, 2013). "Monday Cable Ratings: 'Home Run Derby' Wins Night + 'Love and Hip Hop: Atlanta', 'Monday Night RAW', 'Hit the Floor' & More". TV by the Numbers. Archived from the original on October 14, 2013. Retrieved July 22, 2013.
Jump up ^ Kondolojy, Amanda (July 30, 2013). "Monday Cable Ratings: 'Love and Hip Hop Atlanta' Wins Night + 'Hit the Floor', 'WWE Raw', 'American Pickers', 'Fast N Loud' & More". TV by the Numbers. Archived from the original on December 14, 2013. Retrieved July 31, 2013.
Jump up ^ Bibel, Sara (August 6, 2013). "Monday Cable Ratings: 'Love & Hip Hop Atlanta' Wins Night, 'T.I. and Tiny', 'Teen Wolf', 'The Fosters', 'Major Crimes', 'Switched at Birth'& More". TV by the Numbers. Retrieved August 7, 2013.
Jump up ^ Bibel, Sara (August 13, 2013). "Monday Cable Ratings: 'Love & Hip Hop Atlanta' Wins Night, 'T.I. & Tiny', 'Major Crimes', 'Teen Wolf', 'Longmire', 'Switched at Birth' & More". TV by the Numbers. Retrieved August 14, 2013.
Jump up ^ Kondolojy, Amanda (August 20, 2013). "Monday Cable Ratings: NFL Preseason Wins Night + 'RAW', 'Basketball Wives', 'TI & Tiny', 'Marrying the Game' & More". TV by the Numbers. Retrieved August 21, 2013.
Jump up ^ Kondolojy, Amanda (August 27, 2013). "Monday Cable Ratings: 'WWE Raw' Wins Night + 'Teen Mom', 'Real Housewives of Orange County', 'Basketball Wives', 'TI & Tiny' & More". TV by the Numbers. Retrieved August 28, 2013.
External links[edit]
List of The Glades episodes on IMDb
List of The Glades episodes at TV.com
The Glades at epguides.com
List of The Glades episodes at TheFutoncritic.com
List of The Glades episodes at MSN.TV
Retrieved from "https://en.wikipedia.org/w/index.php?title=List_of_The_Glades_episodes&oldid=817314788"
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Cat (zodiac)
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The Cat is the fourth animal symbol in the 12-year cycle of the Vietnamese zodiac and Gurung zodiac, taking place of the Rabbit in the Chinese zodiac.[1] As such, the traits associated with the Rabbit are attributed to the cat. Cats are in conflict with the Rat.
Legends relating to the order of the Chinese zodiac often include stories as to why the cat was not included among the twelve. Because the Rat tricked the cat into missing the banquet with the Jade Emperor, the cat was not included and was not aware that the banquet was going on and was not given a year, thus began the antipathy between cats and Rats. It is possible domesticated cats had not proliferated through China at the zodiac's induction.[2]
There have been various explanations of why the Vietnamese, unlike all other countries who follow the Sino lunar calendar, have the cat instead of the Rabbit as a zodiac animal. The most common explanation is that the ancient word for Rabbit (Mao) sounds like cat (Meo). [3]
References[edit]
Jump up ^ Tamu (Gurung) Losar Festival
Jump up ^ "Why no year of the Cat?".
Jump up ^ "Year of the Cat OR Year of the Rabbit?". www.nwasianweekly.com. Retrieved 2016-02-23.
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Chlorofluorocarbon
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Chlorofluorocarbons (CFCs) are fully halogenated paraffin hydrocarbons that contain only carbon, chlorine, and fluorine, produced as volatile derivative of methane, ethane, and propane. They are also commonly known by the DuPont brand name Freon. The most common representative is dichlorodifluoromethane (R-12 or Freon-12). Many CFCs have been widely used as refrigerants, propellants (in aerosol applications), and solvents. Because CFCs contribute to ozone depletion in the upper atmosphere, the manufacture of such compounds has been phased out under the Montreal Protocol, and they are being replaced with other products such as hydrofluorocarbons (HFCs)[1] (e.g., R-410A) and R-134a.[2][3]
Contents
[hide]
1 Structure, properties and production
2 Reactions
3 Applications
4 Classes of compounds, nomenclature
4.1 Numbering system
5 History
5.1 Commercial development and use
5.2 Regulation
5.2.1 Regulatory gap
5.2.2 Regulation and DuPont
5.3 Phasing-out of CFCs
5.4 Development of alternatives for CFCs
6 Environmental impacts
7 Tracer of ocean circulation
7.1 CFC and SF6 tracer-derived age of ocean water
7.1.1 Partial pressure and ratio dating techniques
8 Safety
9 References
10 External links
Structure, properties and production[edit]
Main article: Organofluorine chemistry
As in simpler alkanes, carbon in the CFCs bonds with tetrahedral symmetry. Because the fluorine and chlorine atoms differ greatly in size and effective charge from hydrogen and from each other, the methane-derived CFCs deviate from perfect tetrahedral symmetry.[4]
The physical properties of CFCs and HCFCs are tunable by changes in the number and identity of the halogen atoms. In general, they are volatile but less so than their parent alkanes. The decreased volatility is attributed to the molecular polarity induced by the halides, which induces intermolecular interactions. Thus, methane boils at −161 °C whereas the fluoromethanes boil between −51.7 (CF2H2) and −128 °C (CF4). The CFCs have still higher boiling points because the chloride is even more polarizable than fluoride. Because of their polarity, the CFCs are useful solvents, and their boiling points make them suitable as refrigerants. The CFCs are far less flammable than methane, in part because they contain fewer C-H bonds and in part because, in the case of the chlorides and bromides, the released halides quench the free radicals that sustain flames.
The densities of CFCs are higher than their corresponding alkanes. In general, the density of these compounds correlates with the number of chlorides.
CFCs and HCFCs are usually produced by halogen exchange starting from chlorinated methanes and ethanes. Illustrative is the synthesis of chlorodifluoromethane from chloroform:
HCCl3 + 2 HF → HCF2Cl + 2 HCl
The brominated derivatives are generated by free-radical reactions of the chlorofluorocarbons, replacing C-H bonds with C-Br bonds. The production of the anesthetic 2-bromo-2-chloro-1,1,1-trifluoroethane ("halothane") is illustrative:
CF3CH2Cl + Br2 → CF3CHBrCl + HBr
Reactions[edit]
The most important reaction[citation needed] of the CFCs is the photo-induced scission of a C-Cl bond:
CCl3F → CCl2F. + Cl.
The chlorine atom, written often as Cl., behaves very differently from the chlorine molecule (Cl2). The radical Cl. is long-lived in the upper atmosphere, where it catalyzes the conversion of ozone into O2. Ozone absorbs UV-B radiation, so its depletion allows more of this high energy radiation to reach the Earth's surface. Bromine atoms are even more efficient catalysts; hence brominated CFCs are also regulated.
Applications[edit]
CFCs and HCFCs are used in a variety of applications because of their low toxicity, reactivity and flammability. Every permutation of fluorine, chlorine and hydrogen based on methane and ethane has been examined and most have been commercialized. Furthermore, many examples are known for higher numbers of carbon as well as related compounds containing bromine. Uses include refrigerants, blowing agents, propellants in medicinal applications and degreasing solvents.
Billions of kilograms of chlorodifluoromethane are produced annually as precursor to tetrafluoroethylene, the monomer that is converted into Teflon.[5]
Classes of compounds, nomenclature[edit]
Chlorofluorocarbons (CFCs): when derived from methane and ethane these compounds have the formulae CClmF4−m and C2ClmF6−m, where m is nonzero.
Hydro-chlorofluorocarbons (HCFCs): when derived from methane and ethane these compounds have the formula CClmFnH4−m−n and C2ClxFyH6−x−y, where m, n, x, and y are nonzero.
and bromofluorocarbons have formulae similar to the CFCs and HCFCs but also include bromine.
Hydrofluorocarbons (HFCs): when derived from methane, ethane, propane, and butane, these compounds have the respective formulae CFmH4−m, C2FmH6−m, C3FmH8−m, and C4FmH10−m, where m is nonzero.
Numbering system[edit]
Main article: refrigerant § Refrigerants by class
A special numbering system is used for fluorinated alkanes, prefixed with Freon-, R-, CFC- and HCFC-, where the rightmost value indicates the number of fluorine atoms, the next value to the left is the number of hydrogen atoms plus 1, and the next value to the left is the number of carbon atoms less one (zeroes are not stated), and the remaining atoms are chlorine.
Freon-12, for example, indicates a methane derivative (only two numbers) containing two fluorine atoms (the second 2) and no hydrogen (1-1=0). It is therefore CCl2F2.
Another, easier equation that can be applied to get the correct molecular formula of the CFC/R/Freon class compounds is this to take the numbering and add 90 to it. The resulting value will give the number of carbons as the first numeral, the second numeral gives the number of hydrogen atoms, and the third numeral gives the number of fluorine atoms. The rest of the unaccounted carbon bonds are occupied by chlorine atoms. The value of this equation is always a three figure number. An easy example is that of CFC-12, which gives: 90+12=102 -> 1 carbon, 0 hydrogens, 2 fluorine atoms, and hence 2 chlorine atoms resulting in CCl2F2. The main advantage of this method of deducing the molecular composition in comparison with the method described in the paragraph above is that it gives the number of carbon atoms of the molecule.
Freons containing bromine are signified by four numbers. Isomers, which are common for ethane and propane derivatives, are indicated by letters following the numbers :
[hide]Principal CFCs
Systematic name
Common/trivial
name(s), code
Boiling point (°C)
Formula
Trichlorofluoromethane Freon-11, R-11, CFC-11 23.77 CCl3F
Dichlorodifluoromethane Freon-12, R-12, CFC-12 −29.8 CCl2F2
Difluoromethane/pentafluoroethane R-410A, Puron, AZ-20 −48.5 50% CH2F2/50% CHF2CF3
Chlorotrifluoromethane Freon-13, R-13, CFC-13 −81 CClF3
Chlorodifluoromethane R-22, HCFC-22 −40.8 CHClF2
Dichlorofluoromethane R-21, HCFC-21 8.9 CHCl2F
Chlorofluoromethane Freon 31, R-31, HCFC-31 −9.1 CH2ClF
Bromochlorodifluoromethane BCF, Halon 1211, H-1211, Freon 12B1 −3.7 CBrClF2
1,1,2-Trichloro-1,2,2-trifluoroethane Freon 113, R-113, CFC-113, 1,1,2-Trichlorotrifluoroethane 47.7 Cl2FC-CClF2
1,1,1-Trichloro-2,2,2-trifluoroethane Freon 113a, R-113a, CFC-113a 45.9 Cl3C-CF3
1,2-Dichloro-1,1,2,2-tetrafluoroethane Freon 114, R-114, CFC-114, Dichlorotetrafluoroethane 3.8 ClF2C-CClF2
1-Chloro-1,1,2,2,2-pentafluoroethane Freon 115, R-115, CFC-115, Chloropentafluoroethane −38 ClF2C-CF3
2-Chloro-1,1,1,2-tetrafluoroethane R-124, HCFC-124 −12 CHFClCF3
1,1-Dichloro-1-fluoroethane R-141b, HCFC-141b 32 Cl2FC-CH3
1-Chloro-1,1-difluoroethane R-142b, HCFC-142b −9.2 ClF2C-CH3
Tetrachloro-1,2-difluoroethane Freon 112, R-112, CFC-112 91.5 CCl2FCCl2F
Tetrachloro-1,1-difluoroethane Freon 112a, R-112a, CFC-112a 91.5 CClF2CCl3
1,1,2-Trichlorotrifluoroethane Freon 113, R-113, CFC-113 48 CCl2FCClF2
1-bromo-2-chloro-1,1,2-trifluoroethane Halon 2311a 51.7 CHClFCBrF2
2-bromo-2-chloro-1,1,1-trifluoroethane Halon 2311 50.2 CF3CHBrCl
1,1-Dichloro-2,2,3,3,3-pentafluoropropane R-225ca, HCFC-225ca 51 CF3CF2CHCl2
1,3-Dichloro-1,2,2,3,3-pentafluoropropane R-225cb, HCFC-225cb 56 CClF2CF2CHClF
History[edit]
Carbon tetrachloride (CCl4) was used in fire extinguishers and glass "anti-fire grenades" from the late nineteenth century until around the end of World War II. Experimentation with chloroalkanes for fire suppression on military aircraft began at least as early as the 1920s. Freon is a trade name for a group of CFCs which are used primarily as refrigerants, but also have uses in fire-fighting and as propellants in aerosol cans. Bromomethane is widely used as a fumigant. Dichloromethane is a versatile industrial solvent.
The Belgian scientist Frédéric Swarts pioneered the synthesis of CFCs in the 1890s. He developed an effective exchange agent to replace chloride in carbon tetrachloride with fluoride to synthesize CFC-11 (CCl3F) and CFC-12 (CCl2F2).
In the late 1920s, Thomas Midgley, Jr. improved the process of synthesis and led the effort to use CFC as refrigerant to replace ammonia (NH3), chloromethane (CH3Cl), and sulfur dioxide (SO2), which are toxic but were in common use. In searching for a new refrigerant, requirements for the compound were: low boiling point, low toxicity, and to be generally non-reactive. In a demonstration for the American Chemical Society, Midgley flamboyantly demonstrated all these properties by inhaling a breath of the gas and using it to blow out a candle[6] in 1930.[7][8]
Commercial development and use[edit]
During World War II, various chloroalkanes were in standard use in military aircraft, although these early halons suffered from excessive toxicity. Nevertheless, after the war they slowly became more common in civil aviation as well. In the 1960s, fluoroalkanes and bromofluoroalkanes became available and were quickly recognized as being highly effective fire-fighting materials. Much early research with Halon 1301 was conducted under the auspices of the US Armed Forces, while Halon 1211 was, initially, mainly developed in the UK. By the late 1960s they were standard in many applications where water and dry-powder extinguishers posed a threat of damage to the protected property, including computer rooms, telecommunications switches, laboratories, museums and art collections. Beginning with warships, in the 1970s, bromofluoroalkanes also progressively came to be associated with rapid knockdown of severe fires in confined spaces with minimal risk to personnel.
By the early 1980s, bromofluoroalkanes were in common use on aircraft, ships, and large vehicles as well as in computer facilities and galleries. However, concern was beginning to be expressed about the impact of chloroalkanes and bromoalkanes on the ozone layer. The Vienna Convention for the Protection of the Ozone Layer did not cover bromofluoroalkanes as it was thought, at the time, that emergency discharge of extinguishing systems was too small in volume to produce a significant impact, and too important to human safety for restriction.
Regulation[edit]
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Since the late 1970s, the use of CFCs has been heavily regulated because of their destructive effects on the ozone layer. After the development of his electron capture detector, James Lovelock was the first to detect the widespread presence of CFCs in the air, finding a mole fraction of 60 ppt of CFC-11 over Ireland. In a self-funded research expedition ending in 1973, Lovelock went on to measure CFC-11 in both the Arctic and Antarctic, finding the presence of the gas in each of 50 air samples collected, and concluding that CFCs are not hazardous to the environment. The experiment did however provide the first useful data on the presence of CFCs in the atmosphere. The damage caused by CFCs was discovered by Sherry Rowland and Mario Molina who, after hearing a lecture on the subject of Lovelock's work, embarked on research resulting in the first publication suggesting the connection in 1974. It turns out that one of CFCs' most attractive features—their low reactivity— is key to their most destructive effects. CFCs' lack of reactivity gives them a lifespan that can exceed 100 years, giving them time to diffuse into the upper stratosphere.[9] Once in the stratosphere, the sun's ultraviolet radiation is strong enough to cause the homolytic cleavage of the C-Cl bond.
NASA projection of stratospheric ozone, in Dobson units, if chlorofluorocarbons had not been banned. Animated version.
By 1987, in response to a dramatic seasonal depletion of the ozone layer over Antarctica, diplomats in Montreal forged a treaty, the Montreal Protocol, which called for drastic reductions in the production of CFCs. On 2 March 1989, 12 European Community nations agreed to ban the production of all CFCs by the end of the century. In 1990, diplomats met in London and voted to significantly strengthen the Montreal Protocol by calling for a complete elimination of CFCs by the year 2000. By the year 2010, CFCs should have been completely eliminated from developing countries as well.
Ozone-depleting gas trends
Because the only CFCs available to countries adhering to the treaty is from recycling, their prices have increased considerably. A worldwide end to production should also terminate the smuggling of this material. However, there are current CFC smuggling issues, as recognized by the United Nations Environmental Programme (UNEP) in a 2006 report titled "Illegal Trade in Ozone Depleting Substances". UNEP estimates that between 16,000–38,000 tonnes of CFCs passed through the black market in the mid-1990s. The report estimated between 7,000 and 14,000 tonnes of CFCs are smuggled annually into developing countries. Asian countries are those with the most smuggling; as of 2007, China, India and South Korea were found to account for around 70% of global CFC production,[10] South Korea later to ban CFC production in 2010.[11] Possible reasons for continued CFC smuggling were also examined: the report noted that many banned CFC producing products have long lifespans and continue to operate. The cost of replacing the equipment of these items is sometimes cheaper than outfitting them with a more ozone-friendly appliance. Additionally, CFC smuggling is not considered a significant issue, so the perceived penalties for smuggling are low. While the eventual phaseout of CFCs is likely, efforts are being taken to stem these current non-compliance problems.
By the time of the Montreal Protocol, it was realised that deliberate and accidental discharges during system tests and maintenance accounted for substantially larger volumes than emergency discharges, and consequently halons were brought into the treaty, albeit with many exceptions.
Regulatory gap[edit]
While the production and consumption of CFCs are regulated under the Montreal Protocol, emissions from existing banks of CFCs are not regulated under the agreement. In 2002, there were an estimated 5,791 kilotons of CFCs in existing products such as refrigerators, air conditioners, aerosol cans and others.[12] Approximately one-third of these CFCs are projected to be emitted over the next decade if action is not taken, posing a threat to both the ozone layer and the climate.[13] A proportion of these CFCs can be safely captured and destroyed.
Regulation and DuPont[edit]
In 1978 the United States banned the use of CFCs such as Freon in aerosol cans, the beginning of a long series of regulatory actions against their use. The critical DuPont manufacturing patent for Freon ("Process for Fluorinating Halohydrocarbons", U.S. Patent #3258500) was set to expire in 1979. In conjunction with other industrial peers DuPont formed a lobbying group, the "Alliance for Responsible CFC Policy," to combat regulations of ozone-depleting compounds.[14] In 1986 DuPont, with new patents in hand, reversed its previous stance and publicly condemned CFCs.[15] DuPont representatives appeared before the Montreal Protocol urging that CFCs be banned worldwide and stated that their new HCFCs would meet the worldwide demand for refrigerants.[15]
Phasing-out of CFCs[edit]
Use of certain chloroalkanes as solvents for large scale application, such as dry cleaning, have been phased out, for example, by the IPPC directive on greenhouse gases in 1994 and by the volatile organic compounds (VOC) directive of the EU in 1997. Permitted chlorofluoroalkane uses are medicinal only.
Bromofluoroalkanes have been largely phased out and the possession of equipment for their use is prohibited in some countries like the Netherlands and Belgium, from 1 January 2004, based on the Montreal Protocol and guidelines of the European Union.
Production of new stocks ceased in most (probably all) countries in 1994.[citation needed] However many countries still require aircraft to be fitted with halon fire suppression systems because no safe and completely satisfactory alternative has been discovered for this application. There are also a few other, highly specialized uses. These programs recycle halon through "halon banks" coordinated by the Halon Recycling Corporation[16] to ensure that discharge to the atmosphere occurs only in a genuine emergency and to conserve remaining stocks.
The interim replacements for CFCs are hydrochlorofluorocarbons (HCFCs), which deplete stratospheric ozone, but to a much lesser extent than CFCs.[17] Ultimately, hydrofluorocarbons (HFCs) will replace HCFCs. Unlike CFCs and HCFCs, HFCs have an ozone depletion potential (ODP) of 0.[18] DuPont began producing hydrofluorocarbons as alternatives to Freon in the 1980s. These included Suva refrigerants and Dymel propellants.[19] Natural refrigerants are climate friendly solutions that are enjoying increasing support from large companies and governments interested in reducing global warming emissions from refrigeration and air conditioning. Hydrofluorocarbons are included in the Kyoto Protocol because of their very high Global Warming Potential and are facing calls to be regulated under the Montreal Protocol[dubious – discuss][20] due to the recognition of halocarbon contributions to climate change.[21]
On 21 September 2007, approximately 200 countries agreed to accelerate the elimination of hydrochlorofluorocarbons entirely by 2020 in a United Nations-sponsored Montreal summit. Developing nations were given until 2030. Many nations, such as the United States and China, who had previously resisted such efforts, agreed with the accelerated phase out schedule.[22]
Development of alternatives for CFCs[edit]
Work on alternatives for chlorofluorocarbons in refrigerants began in the late 1970s after the first warnings of damage to stratospheric ozone were published.
The hydrochlorofluorocarbons (HCFCs) are less stable in the lower atmosphere, enabling them to break down before reaching the ozone layer. Nevertheless, a significant fraction of the HCFCs do break down in the stratosphere and they have contributed to more chlorine buildup there than originally predicted. Later alternatives lacking the chlorine, the hydrofluorocarbons (HFCs) have an even shorter lifetimes in the lower atmosphere.[17] One of these compounds, HFC-134a, is now used in place of CFC-12 in automobile air conditioners. Hydrocarbon refrigerants (a propane/isobutane blend) are also used extensively in mobile air conditioning systems in Australia, the USA and many other countries, as they have excellent thermodynamic properties and perform particularly well in high ambient temperatures.
One of the natural refrigerants (along with ammonia and carbon dioxide), hydrocarbons have negligible environmental impacts and are also used worldwide in domestic and commercial refrigeration applications, and are becoming available in new split system air conditioners.[23] Various other solvents and methods have replaced the use of CFCs in laboratory analytics.[24]
In Metered-dose inhalers (MDI), a non-ozone effecting substitute was developed as a propellant, known as "hydrofluoroalkane."[25]
Applications and replacements for CFCs
Application
Previously used CFC
Replacement
Refrigeration & air-conditioning CFC-12 (CCl2F2); CFC-11(CCl3F); CFC-13(CClF3); HCFC-22 (CHClF2); CFC-113 (Cl2FCCClF2); CFC-114 (CClF2CClF2); CFC-115 (CF3CClF2); HFC-23 (CHF3); HFC-134a (CF3CFH2); HFC-507 (a 1:1 azeotropic mixture of HFC 125 (CF3 CHF2) and HFC-143a (CF3CH3)); HFC 410 (a 1:1 azeotropic mixture of HFC-32 (CF2H2) and HFC-125 (CF3CF2H))
Propellants in medicinal aerosols CFC-114 (CClF2CClF2) HFC-134a (CF3CFH2); HFC-227ea (CF3CHFCF3)
Blowing agents for foams CFC-11 (CCl3F); CFC 113 (Cl2FCCClF2); HCFC-141b (CCl2FCH3) HFC-245fa (CF3CH2CHF2); HFC-365 mfc (CF3CH2CF2CH3)
Solvents, degreasing agents, cleaning agents CFC-11 (CCl3F); CFC-113 (CCl2FCClF2) None
Environmental impacts[edit]
As previously discussed, CFCs were phased out via the Montreal Protocol due to their part in ozone depletion. However, the atmospheric impacts of CFCs are not limited to its role as an active ozone reducer. This anthropogenic compound is also a greenhouse gas, with a much higher potential to enhance the greenhouse effect than CO2.
Infrared absorption bands trap heat from escaping earth's atmosphere. In the case of CFCs, the strongest of these bands are located in the spectral region 7.8–15.3 µm [26] – referred to as an atmospheric window due to the relative transparency of the atmosphere within this region.[27] The strength of CFC bands and the unique susceptibility of the atmosphere, at which the compound absorbs and emits radiation, are two factors that contribute to CFCs' "super" greenhouse effect.[28] Another such factor is the low concentration of the compound. Because CO2 is close to saturation with high concentrations,[clarification needed] it takes more of the substance to enhance the greenhouse effect. Conversely, the low concentration of CFCs allow their effects to increase linearly with mass.[28]
Tracer of ocean circulation[edit]
Because the time history of CFC concentrations in the atmosphere is relatively well known, they have provided an important constraint on ocean circulation. CFCs dissolve in seawater at the ocean surface and are subsequently transported into the ocean interior. Because CFCs are inert, their concentration in the ocean interior reflects simply the convolution of their atmospheric time evolution and ocean circulation and mixing.
CFC and SF6 tracer-derived age of ocean water[edit]
Chlorofluorocarbons (CFCs) are anthropogenic compounds that have been released into the atmosphere since the 1930s in various applications such as in air-conditioning, refrigeration, blowing agents in foams, insulations and packing materials, propellants in aerosol cans, and as solvents.[29] The entry of CFCs into the ocean makes them extremely useful as transient tracers to estimate rates and pathways of ocean circulation and mixing processes.[30] However, due to production restrictions of CFCs in the 1980s, atmospheric concentrations of CFC-11 and CFC-12 has stopped increasing, and the CFC-11 to CFC-12 ratio in the atmosphere have been steadily decreasing, making water dating of water masses more problematic.[30] Incidentally, production and release of sulfur hexafluoride (SF6) have rapidly increased in the atmosphere since the 1970s.[30] Similar to CFCs, SF6 is also an inert gas and is not affected by oceanic chemical or biological activities.[31] Thus, using CFCs in concert with SF6 as a tracer resolves the water dating issues due to decreased CFC concentrations.
Using CFCs or SF6 as a tracer of ocean circulation allows for the derivation of rates for ocean processes due to the time-dependent source function. The elapsed time since a subsurface water mass was last in contact with the atmosphere is the tracer-derived age.[32] Estimates of age can be derived based on the partial pressure of an individual compound and the ratio of the partial pressure of CFCs to each other (or SF6).[32]
Partial pressure and ratio dating techniques[edit]
The age of a water parcel can be estimated by the CFC partial pressure (pCFC) age or SF6 partial pressure (pSF6) age. The pCFC age of a water sample is defined as:
p C F C = [ C F C ] F ( T , S ) {\displaystyle pCFC={\frac {[CFC]}{F(T,S)}}}
where [CFC] is the measured CFC concentration (pmol kg−1) and F is the solubility of CFC gas in seawater as a function of temperature and salinity.[33] The CFC partial pressure is expressed in units of 10–12 atmospheres or parts-per-trillion (ppt).[34] The solubility measurements of CFC-11 and CFC-12 have been previously measured by Warner and Weiss[34] Additionally, the solubility measurement of CFC-113 was measured by Bu and Warner[35] and SF6 by Wanninkhof et al.[36] and Bullister et al.[37] Theses authors mentioned above have expressed the solubility, F, at a total pressure of 1 atm as:
ln  F = a 1 + a 2 ( 100 T ) + a 3 ln  ( T 100 ) + a 4 ( T 100 ) 2 + S [ b 1 + b 2 ( T 100 ) + b 3 ( T 100 ) ] {\displaystyle \ln F=a_{1}+a_{2}\left({\frac {100}{T}}\right)+a_{3}\ln \left({\frac {T}{100}}\right)+a_{4}\left({\frac {T}{100}}\right)^{2}+S\left[b_{1}+b_{2}\left({\frac {T}{100}}\right)+b_{3}\left({\frac {T}{100}}\right)\right]}
where F = solubility expressed in either mol l−1 or mol kg−1 atm−1, T = absolute temperature, S = salinity in parts per thousand (ppt), a1, a2, a3, b1, b2, and b3 are constants to be determined from the least squares fit to the solubility measurements.[35] This equation is derived from the integrated Van 't Hoff equation and the logarithmic Setchenow salinity dependence.[35]
It can be noted that the solubility of CFCs increase with decreasing temperature at approximately 1% per degree Celsius.[32]
Once the partial pressure of the CFC (or SF6) is derived, it is then compared to the atmospheric time histories for CFC-11, CFC-12, or SF6 in which the pCFC directly corresponds to the year with the same. The difference between the corresponding date and the collection date of the seawater sample is the average age for the water parcel.[32] The age of a parcel of water can also be calculated using the ratio of two CFC partial pressures or the ratio of the SF6 partial pressure to a CFC partial pressure.[32]
Safety[edit]
According to their material safety data sheets, CFCs and HCFCs are colorless, volatile, toxic liquids and gases with a faintly sweet ethereal odor. Overexposure at concentrations of 11% or more may cause dizziness, loss of concentration, central nervous system depression and/or cardiac arrhythmia. Vapors displace air and can cause asphyxiation in confined spaces. Although non-flammable, their combustion products include hydrofluoric acid, and related species.[38] Normal occupational exposure is rated at 0.07% and does not pose any serious health risks.[39]
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External links[edit]
Gas conversion table
Nomenclature FAQ
Numbering scheme for Ozone-Depleting Substances and their substitutes
Class I Ozone-Depleting Substances
Class II Ozone-Depleting Substances (HCFCs)
CFC illegal trade
History of halon-use by the US Navy
Ozone Loss: The Chemical Culprits
Process using pyrolysis in an ultra high temperature plasma arc, for the elimination of CFCs
[1] Environmental Investigation Agency: Reports etc. on illegal trade and solutions
[2] Environmental Investigation Agency in the USA: Reports etc. on illegal trade and solutions
Freon in car A/C
[3] Phasing out halons in extinguishers
[show]
v
t
e
Halomethanes
Monosubstituted
CH3F
CH3Cl
CH3Br
CH3I
Disubstituted
CH2F2
CH2ClF
CH2BrF
CH2FI
CH2Cl2
CH2BrCl
CH2ClI
CH2Br2
CH2BrI
CH2I2
Trisubstituted
CHF3
CHClF2
CHBrF2
CHF2I
CHCl2F
C*HBrClF
C*HClFI
CHBr2F
C*HBrFI
CHFI2
CHCl3
CHBrCl2
CHCl2I
CHBr2Cl
C*HBrClI
CHClI2
CHBr3
CHBr2I
CHBrI2
CHI3
Tetrasubstituted
CF4
CClF3
CBrF3
CF3I
CCl2F2
CBrClF2
CClF2I
CBr2F2
CBrF2I
CF2I2
CCl3F
CBrCl2F
CCl2FI
CBr2ClF
C*BrClFI
CClFI2
CBr3F
CBr2FI
CBrFI2
CFI3
CCl4
CBrCl3
CCl3I
CBr2Cl2
CBrCl2I
CCl2I2
CBr3Cl
CBr2ClI
CBrClI2
CClI3
CBr4
CBr3I
CBr2I2
CBrI3
CI4
CAt4
* Chiral compound.
[show]
v
t
e
Functional groups
Only carbon,
hydrogen
and oxygen
Hydrocarbons
Allene
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Ester
Ether
Ethylenedioxy
Hydroxy
Ketone
Methylenedioxy
Peroxide (Organic)
Ynone
Only one
element
apart from
C, H, O
Nitrogen
Amine
Azo compound
Cyanate
Hydrazone
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Imine
Isocyanate
Isonitrile
Nitrene
Nitrile
Nitro compound
Nitroso compound
Organic amide
Oxime
Phosphorus
Phosphonate
Phosphonous
Sulfur
Disulfide
Sulfone
Sulfonic acid
Sulfoxide
Thial
Thioester
Thioether
Thioketone
Thiol
Selenium
Selenol
Selenonic acid
Seleninic acid
Selenenic acid
Tellurium
Tellurol
Other
Isothiocyanate
Phosphoramide
Sulfenyl chloride
Sulfonamide
Thiocyanate
See also chemical classification, chemical nomenclature (inorganic, organic)
[show]
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