Long before Cheryl, Posh and Scott Carson's girlfriend tore it up in Baden-Baden, Wags were having an impact upon the World Cup. Frank Arnesen's sending-off, which contributed to Denmark's sad exit from Mexico 86 , was the consequence of serious concern for his wife's health (this vicious tackle, after a breathtaking piece of skill, didn't put him in the best of moods either, but we digress). And four years later Frank Rijkaard's infamous contretemps with Rudi Völler was apparently sparked because of the breakdown of his marriage just before the tournament.

There have been 159 red cards in the World Cup but it is hard to believe that anyone has misplaced the plot to this extent. Let's recap. Rijkaard scythed down Völler and sniggered like a naughty schoolboy when he was booked. He then defiled Völler's mullet with spittle – very few people noticed at the time, although the BBC's Tony Gubba did – as he ran past. From the resulting free-kick, after Völler pulled out of a tackle with Hans van Breukelen and fell over, Rikjaard lumbered over and shaped to lift Völler by the ear. At this stage Rijkaard was still only on a yellow card, and might have got away with the whole thing, but the context of a World Cup knockout game against Holland's fiercest rivals (in a World Cup qualifier a year earlier, a banner had jauntily compared Lothar Matthäus to Adolf Hitler) was secondary to the urgent need to flob at Völler a second time.

As Völler was stumbling to his feet, about to receive the most unjust punishment in the history of mankind, Rijkaard furiously horked every last particle of phlegm from the deepest recesses of his sinuses, attempting to set an unofficial world record for mucus thickness. It's an astonishing sight . Then, when both men were sent off, Rijkaard finished the job, nonchalantly gobbing into Völler's hair like a jogger aiming at a lamppost, and breezily fled the scene faster than you could say "noggin's gone". Völler stood still, the personification of affronted confusion. He might well have thought the whole thing was some elaborate Truman Show-style wind-up, but he took his red card with staggering dignity. If anyone was entitled to some red mist it was Völler.

On the BBC highlights programme that night, Ray Wilkins thought of the children. "Young kids, y'know … please, parents, turn the videos off now because that is just absolutely scandalous." It was even more unfathomable because Rijkaard was usually such a, well, phlegmatic character; a gentle soul and a good man.

He apologised to Völler a few months later and in 1996 the pair adorned cream dressing gowns and shared breakfast in an advert for a butter company. "The fee was donated by both of us to charity, otherwise I wouldn't have joined in," Völler said in this interview. His enduring beef is not so much with Rijkaard but the referee, Juan Carlos Loustau. "I still can't understand why the ref sent me off, and I guess he will take it to his grave." So will Völler and Rijkaard, whose brilliant careers were arguably defined by that one moment of weirdness. RS

2) Tommy Gemmell v Helmut Haller, October 1969

Here's one of the all-time classics, a piece of film that could only be bettered were it set to a Flintstones soundtrack. Yes, it's Scotland's Tommy Gemmell toe-punting West Germany's Helmut Haller up the fundament in a 1969 World Cup qualifier.

Haller had sent Reinhard Libuda clear to score the decisive goal in a 3-2 win in Hamburg on 79 minutes, but it was not the midfielder's last act of the match. With time running out and the Scots desperate to at least equalise, Gemmell cut inside from the left only to have his leg cynically swiped by Haller. [FX: Barney Rubble's Big Head Take] There's the briefest of pauses as the mist descends on Gemmell. As the Scot turns in the determined fashion, Haller suddenly realises what he's done, and attempts to exit the scene in one piece. [FX: Fred Flintstone Scrambling] No such luck, son. Ooyah! Oof! [FX: Fred Drops The Ball].

But it wasn't all cartoon capers. Gemmell's club manager, Jock Stein, had been in the stands watching, and sat on the plane home in a low seethe. He dropped Gemmell for the following weekend's League Cup final against St Johnstone, Davie Hay taking his place and his winners' medal. Gemmell put in a transfer request, and though the Lisbon Lion would remain at Celtic for two more years, scoring in the 1970 European Cup final just as he had done in 1967, his relationship with Stein would never recover and he eventually left for Nottingham Forest. "If it hadn't been for Haller," reminisced Gemmell after the German's death last year, "there is every chance I would never have left Celtic. Although I wanted to kick him over the stand that night, I am sad at his passing." SM

Gary Bennett is a Sunderland legend for a number of reasons: 11 years of languid defensive excellence, 440-odd games, one famous goal. But mainly for his services to fan/player interaction via the medium of David Speedie's throat.

Speedie was a footballer who loved to be hated. He spent his career winding up opponents and fans for – and with – kicks, sometimes obscuring a considerable talent in the process. "Speedie is a prick," says one comment on an alternative YouTube video of this incident. "I would know. He's my uncle."

His relationship with Bennett began after the first leg of the 1985 League Cup semi-final between Sunderland and Chelsea, when Bennett and Howard Gayle had a zealous exchange of views with Speedie's father in the players' lounge at Roker Park. Five years later, Sunderland met Speedie's Coventry in the quarter-finals of the same competition. Bennett had a bad knee and probably shouldn't have been playing, and as centre-half and centre-forward he and Speedie exchanged the usual unpleasantries in the course of their work.

Matters came to a head when a loose ball broke towards the touchline. Speedie went miles over the top of the ball, leaving a snide one on Bennett's bad knee. As his momentum took him towards the Sunderland fans in the Clock Stand – no fencing in those days, remember – Speedie tilted his head theatrically to the side and stood statuesque while staring into the middle distance. He was a picture of misplaced pride, with the self-satisfied pose of somebody who thinks he's won hands down – oblivious to the fact that, behind him, a hand was going up, the chickens not so much coming home to roost as to whip off his wattle. Bennett's tensed, open hand homed inexorably in on Speedie's neck, like a scene in a horror movie where the audience can see what's coming but the protagonist has no idea.

Bennett, for a split-second consumed with a hate supreme, was intent on some vigilante justice: he eased Speedie over the advertising hoardings into a disappointingly benevolent crowd. The ITV commentator John Helm, used to a culture in which ABH usually only merited a stern talking-to, said the referee "will have very strong words with the Sunderland captain about this". In fact he sent both Bennett and Speedie off.

"To be honest I just saw red," said Bennett in this interview. "Goodness knows what might have happened if the officials hadn't pulled me away. In fact at one point he ended up in the crowd but they just kept pushing him back. When supporters ask me about David Speedie I always tell them: 'It's your fault, you lot could have sorted him out once and for all that night!'" RS

There is a superbly perceptive section in Paul McGrath's autobiography in which he describes the unspoken dance between centre-half and centre-forward as they battle for supremacy, the balance of power changing almost imperceptibly throughout a match. It applied more in McGrath's time, when teams played two up and each centre-back took a man. Theirs was a unique relationship, not least because they were in constant competition yet scarcely ever in a position to stare awkwardly at each others' eyebrows, never mind the whites of their eyes. There were so many ways you might exert superiority. Strength, skill, subtlety, sleight of foot or sleight of hip, all geared towards the decisive breaking of your opponent's will.

Or you could just boot him unfairly and squarely in the trousers.

All the YouTube videos of Mark Hughes, all those furious finishes, remind us how big a sweet spot existed on his right boot. It was not as big as the tender spot between David Tuttle's legs, upon which Hughes homed with rare decisiveness after miscontrolling a ball over the top from Denis Irwin. "When I viewed the game on video late that night I couldn't believe what I was seeing," said Sir Alex Ferguson in Managing My Life. "Hughes had almost dislodged Tuttle's testicles."

The beautiful thing about this is its almost entire pointlessness: with two minutes to go the game was pretty much safe, thanks to a quite glorious goal from Hughes – "If we've got any chance in international football, this has to be the way to score goals," plus-ça-changed the co-commentator Trevor Brooking – and Tuttle had done little beyond exhibiting the usual assertions of masculinity written into a centre-half's contract in the early 1990s. There was a bad, unpunished foul on Hughes 16 minutes earlier but that was par for the course.

No matter. As the ball drifted towards the corner flag, Hughes suddenly contracted an almost lethal dose of the battle fever. In the future words of his team-mate Roy Keane, he stuck it up Tuttle's bollocks. And then had the gall to complain, as did Ryan Giggs, who stopped just short of pleading that Hughes had got the ball. In those days, it was only a second yellow card. Tuttle probably had a couple of yellows as well. RS

5) Roy Keane v Alan Shearer, September 2001

Keane is mainly remembered these days – this is purely in the context of transgressing football's laws, he achieved one or two other things in the game after all – for his cold-blooded assassination of the Manchester City midfielder Alf Inge Haaland in 2001. A modern take on Big Jack Charlton's Little Black Book, Keane had made a mental note of Haaland who, four years earlier and then at Leeds, sneered over him as he rolled around in pain with a snapped cruciate ligament. "Bryan Robson had told me to take my time," Keane later recalled. "'You'll get your chance, Roy. Wait.'"

Wait he did. And the calm and calculating nature of the eventual payback – "Alfie was taking the piss. I'd waited long enough. I fucking hit him hard. The ball was there (I think). Take that, you cunt" – is usually the first point of reference when it comes to Keane and the darker arts these days. But it rather obscures the fact that the whole episode was set off after Haaland had piqued Keane in that fateful 1997 brouhaha with a masterclass in niggly fouls, to the extent that the Manchester United man knacked himself while attempting a retaliation. ("I was trying to trip him up rather than kick him," explained Keane. "I knew it would probably mean a booking, but fuck it.") The 2001 Haaland hit was an aberration; the majority of Keane's mistakes were made while out of control on a rolling boil, his brain very much melting in a bain-marie of belligerence.

Keane has contributed quite a few classics to the canon, from tap-dancing on Gareth Southgate's titties in the 1995 FA Cup semi-final to losing a battle of minds with Alan Shearer at Newcastle in 2002. ("Shearer stops me taking the throw in," begins his account in the Eamon Dunphy-ghosted Keane. "He's taking the piss. I lose it, throw the fucking ball at him. 'You prick,' he sneers. The way he says it, I know he really means it. I go for him, try to grab him by the throat. He's grinning. 'You prick,' he gestures dismissively. The red card comes out. Shearer's right. I am a prick. Fell into the trap.")

But here's one that's oft-forgotten these days. It's October 1995, and Eric Cantona is four games back after the eight-month absence enforced for his kung-fu clean-out of that clown at Crystal Palace. United are hosting Middlesbrough, and on 18 minutes Nigel Pearson makes a two-footed lunge at Cantona, no doubt a warm and witty homage to the French striker's Selhurst Park shenanigans. Cantona bats not an eyelid. "Since returning," reported David Lacey in this paper, "Cantona has yet to give an opponent a dirty look."

However, Keane had clearly decided to take up Eric's slack. Running the length of the pitch to instigate a Hegelian dialectic with Middlesbrough's players and the referee, and having then offered a trenchant antithesis to Pearson's thesis, he became frustrated at the lack of a third way. Which may explain why he "followed this up with a wild hack at a passing opponent", then 12 minutes later responded to Jan Aage Fjortoft tugging at his shirt by extending his right arm and attempting to push the Boro striker's face through. Off you go!

The game was scoreless at the time, but the ten men of United went on to win 2-0. It was Keane's third sending off in a United shirt - he had walked for the aforementioned Southgate incident and then for a dive at Blackburn - and each time his team went on to win the game. "Perhaps their handicap should be re-examined," was Lacey's tinder-dry assessment. SM

6) Humberto Maschio v Honorindo Landa, June 1962

The fixture between Chile and Italy in Group Two of the 1962 World Cup should be considered not so much a football match, more the statistical outlier in a centuries' worth of meteorological data, a unique atmospheric convergence of red mist which hovered over Santiago for an unprecedented 90 minutes (plus the eight minutes of first-half stoppage time which accounted for the bobbies coming on mob-handed to drag Georgio Ferrini off).

Picking one particular example of misto rosso from a game that featured several haymakers, a couple of broken noses, one acrobatic hoof in the coupon, a rugby tackle, and the forced removal of a player by several members of the local filth, is a futile affair. Not least because all the set-piece rumbles are so well known, and we'd be arguing all day over which one is the most entertaining. So instead let's pick a moment for the red-mist purist which occurred right at the end of the first half.

The Argentinian-born Italian midfielder Humberto Maschio had already (1) been shoved in the chest and (2) punched in the face, (3) and had punched someone in the face, and (4) raked his studs down a Chilean shin. Italy were down to nine men by this point, although, as the referee Ken Aston hadn't considered Maschio one of the worst offenders, he was free to continue playing. With seconds of the half remaining, he was brought down by Chile's captain, Sergio Navarro. It was a free-kick. Eladio Rojas, jogging slowly back to defend, did what players do and flicked the static ball back upfield a couple of yards into empty space, in an attempt to lessen Italy's advantage. Play hadn't restarted but the referee's whistle in Maschio's head blew loud and clear. He raced back after the ball, but instead of calmly retrieving and replacing it, slid across the turf and hoicked it violently out of play for a "throw". His fuses blown, there he was, doing battle with invisible opponents on the biggest stage of all.

This occurred at the end of a 53-minute half packed with so much ultraviolence that Maschio, a constant presence as both victim and perpetrator, had been propelled by righteous indignation, anger and ear steam into uncharted mental territory. He had found himself rocket-blasting through several layers in the mist-o-sphere with the controls of the funk mothership set for the heart of the sun. Most folk, no matter how annoyed, come back down to earth after a moment or two. Like panic attacks and erections, you can only keep it going for so long. But he'd been at it for nearly an hour. He really was out there. And this is what happens to a man. This is red mist in its most condensed form, a distillation of disintegration, a tantrum tincture.

Luckily, half-time was upon him, during which a damp cloth to the napper could be applied. And by golly it worked, for Maschio was a much more measured gent during the second period. At the final whistle came happy evidence that his mind was working clearly again, and no lasting damage had been done. He offered his hand to Honorino Landa, and as the two shook in the sporting fashion, slyly crunched his other fist on to his opponent's jaw. [FX: Yogi Bear's Noggin Klonk] SM

• The inconsistent spelling of Tommy Gemmell's surname was corrected on Friday 29 November 2013